Hybrid liquid toners

ABSTRACT

A hybrid liquid toner composed of a mixture of two different types of liquid toner. One type is a liquid toner that includes a complex amphipathic molecule of which at least a fixer and a dispersant are polymeric moieties and which additionally includes a charge director and optionally includes a color agent, all of these being carried by a volatile organic solvent of high electrical resistivity. The other type of liquid toner is one that includes a fixer and a dispersant as separate chemical entities and further includes a charge director, a pigment type color agent and a carrier solvent such as mentioned above. The two toners can be mixed in a very wide range of proportions and when so mixed have several advantages which makes the hybrid toner particularly useful in connection with preparation of lithographic masters and microfiche reproductions by electrostatography as well as useful as an all purpose liquid toner.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is a division of application Ser. No. 433,251 filedJan. 14, 1974 for HYBRID LIQUID TONERS, the latter application being animprovement over applications Serial No. 810,841 (now abandoned) filedMar. 26, 1969 for LIQUID TONERS, and Ser. No. 7253 filed Jan. 30, 1970for LIQUID TONERS (now U.S. Pat. No. 3,753,760 dated Aug. 21, 1973); andis a continuation of application Ser. No. 163,502 (now abandoned) filedJuly 16, 1971 for HYBRID LIQUID TONERS.

BACKGROUND OF THE INVENTION

1. Field of the Invention

A hybrid liquid toner composed of a mixture of two toners, one of whichincludes an amphipathic molecule composed of various polymeric moietieshaving different functions at least one of which is a fixing functionand another is a dispersant function, and a second liquid toner whichincludes no amphipathic molecule but does include a fixer and adispersant as separate chemical entities, preferably at least one of thetoners including a color agent, and the hybrid toner further including acharge director, and an organic volatile liquid carrier solvent of highelectrical resistivity.

2. Description of the Prior Art

A conventional prior art liquid toner typically was composed of avolatile organic liquid solvent system of high electrical resistivity inwhich there were carried several constituents, some being dispersed andothers being dispersed or solvated. Exemplificatively, these otherconstituents were: a thermoplastic fixer, a dispersant, a pigment whichfrequently was carbon black, and a charge director, all of these beingseparate chemical entitles. This type of prior art toner will bereferred to hereinafter as a "first" liquid toner.

A second type of liquid toner has been proposed in application Ser. No.810,841 (now abandoned) filed Mar. 26, 1969 for LIQUID TONERS, and inapplication Ser. No. 7253 filed Jan. 30, 1970 for LIQUID TONERS (nowU.S. Pat. No. 3,753,760) which is a continuation-in-part of applicationSer. No. 810,841. This latter liquid toner will hereinafter be referredto as the "second" liquid toner. The second liquid toner wascharacterized by the presence therein of an amphipathic molecule whichas at least one polymeric moiety thereof included a thermoplastic fixerand as at least another polymeric thereof a dispersant plastic fixer andas at least another polymeric thereof a dispersant so that these twomoieties formed part of a single chemical entity which was complexmolecule. The amphipathic molecule could also include as anotherpolymeric moiety thereof a color agent or the color agent could be achemically separate entity in the second liquid toner. Furthermore, thesecond liquid toner included a charge director which was not part of theamphipathic molecule. Like the first liquid toner, the second liquidtoner additionally included a liquid carrier which was a volatileorganic solvent system of high electrical resistivity. Of the said onepolymeric moiety and the said another polymeric moiety, at least one isthermoplastic. The said one polymeric moiety is soluble in the solventsystem and a portion thereof is a fixative and a dispersant. The saidanother polymeric moiety is insoluble in the solvent system and has aparticle size between 25 mμ and 25μ, a portion of said another polymericmoiety being a fixative. Thereby the second type of liquid toner has acontinuous phase constituting the solvent system with the said polymericmoiety dissolved therein and a dispersed phase constituting the saidanother polymeric moiety so that the amphiphathic molecule acts as amono-dispersed particle phase, a fixative and a dispersant.

Each of these two liquid toners had certain advantages and each hadcertain disadvantages, the disadvantages of the second liquid tonerbeing comparatively minor but nevertheless existent. Thesedisadvantages, and particularly the disadvantages of the second liquidtoner, were not important factors in the use of the second liquid tonerfor most electrostatographic purposes such, for instance, as one of themost widespread applications thereof which constituted its employment inan office copying machine. However, the minor disadvantages of thesecond liquid toner did to some extent hinder its use in connection withthe preparation of lithographic masters and of reproductions formicrofiche purposes by an electrostatographic process.

Thus, it has been found that where the second liquid toner was used formaking a lithographic master, although the master could be used for alarge number of runs, for instance over 15,000, when the runs wereconsiderably longer there was a tendency for the electrostatographicallydeposited image to deteriorate.

Electrostatographic lithographic masters are prepared byelectrostatographically depositing a toner either with or without acolor-agent on a flexible base which is covered with a photoconductorcoating that has had formed therein a latent electrostatic image andsubsequently is developed by applying a liquid toner thereto. Both thephotoconductor coating and the deposited toner image are oleophilic andto render the image and its carrier useful as a master the backgroundareas having no deposits thereon must be rendered oleophobic which isaccomplished by making them hydrophilic. This transformation is effectedby a swabbing technique which, for example, employs a water solution offerrocyanide or ferricyanide as an etchant that attacks the portion ofthe photoconductor coating which does not bear theelectrostatographically deposited image. The photoconductorconventionally used in this technique is zinc oxide in a resin binder,this being a commercial electrostatographic paper.

In connection with the preparation of lithographic masters (as well asfor general purposes) with the use of the first liquid toner, a seriousdisadvantage was present which occurred where the original to bereproduced contained one or more colored (non-white) areas ofappreciable size, for instance in excess of 1/4inch in any dimension. Insuch cases there was a marked tendency for the deposit of toner on thearea to be of greater density adjacent the periphery than at the center.This drawback did not attend the use of the second liquid toner.

As to electrostatographic microfiche reproductions there was a minordisadvantage accompanying the use of the second liquid toner which wasthat there was a tendency, which might be caused by the large size ofthe complex molecule, for the boundary line of the image to waverslightly, i.e. to deviate slightly and almost unnoticeably from afaithful reproduction of the boundary line of the original. thisdisadvantage affected the ability to form a good enlargement of themicrofiche image.

A far more serious disadvantage associated with the use ofelectrostatographic reproduction of microfiche images and which wasinherent in the use of the first liquid toner was the difficulty infixing the electrostatographically deposited image on the carrier. Thecarrier included a transparent thermoplastic filmforming materialcontaining a transparent photoconductor which was utilized to form thelatent electrostatic image, the same subsequently being developed. Onesuch photoconductor which was widely used was a poly-N-vinyl carbazole.After the image had been deposited it had to be fixed. This fixing wasaccomplished by heating, but, since the film-forming material tended tobecome dimensionally unstable at approximately the temperature employedfor fusing the image, there was a marked tendency for the image todistort which was unacceptable for microfiche luses.

SUMMARY OF THE INVENTION

1. Purposes of the Invention

It is an object of the present invention to provide an unique hybridliquid toner which is not subject ot any of the foregoing defects.

It is another objects of the invention to provide a hydrib liquid tonerwhich is capable of being employed in electrostatographic formation of alithographic master that is capable of extended runs, well in excess of15,000 reproductions, without deterioration.

It is another object of the invention to provide a hybrid liquid tonerof the character described which has a good "fill" of solid-coloredareas and yet is capable of being treated to enable the same to be usedas a lithographic master.

It is another object of the invention to provide a hydrid liquid tonerof the character described which is particularly useful for thepreparation of microfiche images by electrostatographic processes andwherein the resolution is exceedingly good and heat fixing can beachieved without disturbing the dimensional stability of the transparentthermoplastic which constitutes the support for the developed image.

It is another object of the invention to provide a hydrid liquid tonerof the character described which, in addition to being useful for theaforesaid purposes, can, without any modification whatsoever, beemployed for conventional office copying purposes in any type ofequipment using a liquid toner, thereby enabling the same toner to beemployed universally for all kinds and types of purposes.

Indeed, it is an ancillary object of the invention to provide a hybridliquid toner of the character described which can be used in any systemin which a liquid toner of any kind can be employed as, for instance, inink jet recording, for cathode ray tube read-outs and in conjunctionwith light beam writing, as well as cathode ray pin tubes and varioustypes of transfer processes such as pressure transfer, vacuum transferand electrostatic transfer.

2. Brief Description of the Invention

In general, the invention is carried out by combining two liquid tonersutilizing, basically, functionally different systems, the two tonersbeing admixable in an extremely wide range of proportions,exemplificatively as little as 0.5% of either the first or second liquidtoner with the balance of the hybrid toner constituting the other liquidtoner. As will be pointed out in the specific description, there arevarious advantages to be gained by adjusting these proportions in eitherdirection.

The first toner is the type which, as of the date of this application,is known as a "conventional" toner and it includes as a liquid carrier avolatile organic solvent system of high electrical resistivity, e.g. atleast about 10⁹ ohms centimeters. This liquid carrier has therein afixer which may either be dispersed or solvated, a dispersant whichusually is solvated, a charge director which may be solvated ordispersed and a pigment such, for instance, as carbon black whichconventionally is dispersed.

The second liquid toner is of the type disclosed in the aforesaid patentapplications Ser. Nos. 810,841 (now abandoned) and 7253 (now U.S. Pat.No. 3,753,760) These generally include a solvent system such as the oneused for the first toner. The solvent system has therein a complexamphipathic molecule that at least includes as polymeric moietiesthereof a fixer and a dispersant and which may include as an additionalmoiety a color agent. The color agent may also be present in the secondtoner as a separate chemical entity, i.e. not part of the complexamphipathic molecule. The color agent is not necessarily present ineither the first or the second liquid toner, although it is desirablyemployed. For example, it does not have to be included if the hybridtoner is to be used exclusively in the formation of a lithographicmaster although, even under such circumstances, its presence isdesirable. Furthermore, the second toner includes a charge directorwhich is not part of the amphipathic molecule.

When the two toners are admixed with the use of any conventional mixingequipment such, for instance, as a blender, a ball mill, a batch stirreror a homogenizer, or even manually stirred, a hybrid toner is createdwhich is particularly useful for forming lithographic masters andmicrofiche reproductions electrostatographically and is also useful as ageneral purpose electrostatographic developer both in ordinary businesscopy machines of all kinds and in the special type of equipmenthereinbefore briefly alluded to, to wit, ink jet printers, cathode raytube printers, light beam writing printers and transfer printers.Instead of preparing the two toners separately and then combining them,the ingredients for both toners can be mixed at the same time. Thehybrid toner preferably includes a common solvent system and may includea common charge director(s) and color agent(s). Furthermore, theamphipathic molecule of the second liquid toner may be used as thedispersant for the first liquid toner.

DESCRIPTION OF THE PREFERRED EMBODIMENTS

Any conventional prior art first liquid toner can be employed. Such atoner includes a volatile organic liquid solvent system having a highelectrical resistivity of at least about 10⁹ ohms centimeters.

Preferably, the solvent system includes one or more solvents of thepetroleum type such a solvent commonly being referred to as a "petroleumfraction". This includes distilation fractions, catalytically crackedfractions and polymers of aliphatic monomers derived eithersynthetically or by distillation or cracking fractionation. Petroleumfractions are particularly useful in connection with the first tonerbecause of the following attributes:

(a) quick evaporation, e.g., a thin film of the carrier will evaporatein a few seconds at a temperature below the char point of paper, so asto permit fast drying; (b) non-toxicity; (c) low odor; (d) thecharacteristic that when employed with soluble solid film-forming agentsit will fully escape therefrom so as to leave the solid film depositedby such agent tack-free and not subject to evaporation over protractedperiods of time after the deposited image is seemingly dry; (e)sufficient fluidity to allow the particles of pigment to migratetherethrough with ease so that the pigment is capable of being quicklyelectrostatically attracted to and coupled with the pattern ofelectrostatic charges which is to be developed; (f) not attacking thecoating binders on a base sheet and not attacking other ingredients ofthe sheet; (g) not bleeding the electrostatic charges before the pigmentis deposited so as to maintain any desired degree of contrast; and (h)inexpensiveness.

In order to obtain these beneficial attributes, the petroleum fraction,i.e., paraffinic solvent, should have an evaporation rate at least asfast as that of kerosene, but slower than that of hexane. Thereby, theevaporation of the liquid from a film will be rapid, e.g., two seconds,at a temperature slightly below the char point of paper, it beingfrequently customary to raise the temperature of the film of liquiddeveloper to this level for the purpose of evaporating the developerafter the opaque electroscopic particles of pigment have been depositedby attraction on the electrostatically charged pattern. The petroleumfraction should have a low K. B. (Kauri-butanol) number, to wit, lessthan 35, and preferably between 26 and 35. This low K. B. numberminimizes the possibility that the petroleum fraction will attack thecoating binder, e.g., the binder for the zinc oxide, or will attack anysizing on the sheet, e.g., paper, upon which the coating is applied. Thepetroleum fraction also should be substantially free of aromatic liquidconstituents, i.e., it should be substantially aromatic-liquid-free.This term, as used herein, connotes that the proportion of aromaticliquids in the organic liquid carrier should not be in excess of two percent by weight. The aromatic liquids have a strong tendency to attackthe coating binders, e.g., the coating binders for zinc oxide, but inconcentrations of less than two per cent this tendency is so negligibleas to be unnoticeable. The petroleum fraction must have a highelectrical resistivity, e.g., in the order of at least about 10⁹ ohmcentimeters, and a dielectric constant of less than three and one-half,so that the liquid carrier will not dissipate the pattern ofelectrostatic charges which are to be developed. The TCC (Tagliabueclosed cup) flash point of the liquid carrier should be at least 100° Fand preferably about 120° to 152° F, whereby under the conditions of usethe liquid is considered non-flammable. The paraffinic solvent also isnon-toxic. It possesses no objectionable odor and preferably isodor-free, this being denoted by the term "low odor". Consonant with itslow dielectric constant and high resistivity, the liquid carrier isnon-polar. The solvent system should have a low viscosity for thepurpose, as indicated above, of permitting rapid migration therethroughof opaque electroscopic charged pigment particles which are to beattracted in large number to the electrostatically charged image whichis to be developed. Such viscosity should be between 0.5 and 2.5centripoises at room temperature. The petroleum fraction also isinexpensive.

Examples of petroleum fraction organic liquid carriers having physicalcharacteristics which fall within the foregoing criteria are Shell Sol71, manufactured by Shell Oil Company; Isopar G, Isopar H, Isopar K, andIsopar L, manufactured by Humble Oil and Refining Company; Amsco OMS,Amsco 460 Solvent and Amsco Odorless Insecticide Base manufactured byAmerican Mineral Spirits Company; and odorless kerosene. All of theforegoing are low odor paraffinic solvents. The dielectric constant ofShell Sol 71 is 2.06 at room temperatures. The other solvents havedielectric constants of the same order of magnitude. Other physicalcharacteristics of Shell Sol 71, Isopar G, Isopar H, Isopar K, Isopar L,Amsco OMS, Amsco 460 Solvent and Amsco Odorless Insecticide Base whichfingerprint these solvents and denote the presence of several of theabove listed attributes are set forth below:

    ______________________________________                                                  Distillation                                                                          Flash Pt.                                                             IBP* Dry End                                                                                                Sp. Gr.                                              Pt.    ° F.                                                                          K.B. Aniline                                                                             60°/60°                           ° F.                                                                        ° F.                                                                          TCC    No.  Pt. ° F.                                                                     F.                                    ______________________________________                                        Shell Sol 71                                                                              345    398    121  26.5 183   0.7563                              Isopar G    318    347    105  28.0 178   0.748                               Isopar H    350    371    123  26.9 183   0.7571                              Isopar K    349    383    126  26.5 185   0.7587                              Isopar L    372    406    144  --   187   0.7674                              Amsco OMS   352    386    125  27.0 184.5 0.7608                              Amsco 460 Solvent                                                                         375    456    150  34.5 146.5 0.8108                              Amsco Odorless                                                                Insecticide Base                                                                          375    482    152  26.5 175.0 0.7711                              ______________________________________                                         *Initial Boiling Point ASTM D-1078                                       

The second constituent of the first liquid toner is the fixer which maybe dispersible or soluble in the organic solvent system. The fixer actsas a film-forming agent in the developed image, holding the pigmentbound to the carrier sheet. The fixing agent is solid at roomtemperatures and in the absence of a solvent therefor. The fixing agent,if soluble in the solvent system, preferably is fully soluble thereinand has a good solvent release characteristic, which is to say, it mustpermit the solvent system to evaporate completely and quickly through asolid coherent film-like deposit left as a residue after solventevaporation. The film left by the fixer either with or without heatingof the deposited fixer, as the case may be, must be tackfree, tough andcoherent so that the developed image will not smear or shred and will beresistent to deterioration. Moreover, the fixer should be compatiblewith the binder for the photoconductor coating, e.g. with the binder fora photoconductor zinc oxide coating, and should bond well to saidcoating in order to avoid any tendency of the finished image to separateor peel from the coated sheet. The following constitute excellentfixers, some of these being of the solvatable type and others being ofthe non-solvatable type:

Resin NC 11, manufactured by Hercules Powder Company. This is a palethermoplastic acidic wood rosin that has been both polymerized andhydrogenated. It has a softening point of 85° to 93° C by the Herculesdrop method and an acid number of 145-65. Its density at 20° c is 1.065.It has a saponification number of 155-165. Its degree of hydrogenationis about 90% and it has an average molecular wieght of 360. About 20% ofthe rosin acids are polymerized.

    ______________________________________                                                                           *                                                 Manu-                  Acid Softening                                  Resin  facturer  Description  No.  Pt. ° C                             ______________________________________                                        Lewisol 7                                                                            Hercules  Glycerol ester                                                                of modified                                                                   wood rosin   8    168 HDM                                    Pentalyn A                                                                           Hercules  Pentaerythritol                                                               ester of wood                                                                 rosin        12   111 HDM                                    Pentalyn C                                                                           Hercules  Pentaerythritol                                                               ester of poly-                                                                merized wood                                                                  rosin        14   135 HDM                                    Pentalyn G                                                                           Hercules  Modified penta-                                                               erythritol ester                                                              of wood rosin                                                                              14   135 HDM                                    Pentalyn H                                                                           Hercules  Pentaerythritol                                                               ester of hydro-                                                               genated wood                                                                  rosin        13   104 HDM                                    Pentalyn K                                                                           Hercules  Pentaerythritol                                                               ester of dimeric                                                              resin acids  14   192 HDM                                    Pentalyn X                                                                           Hercules  Modified penta-                                                               erythritol ester                                                              of wood rosin                                                                              14   159 HDM                                    Pentalyn                                                                             Hercules  Pentaerythritol                                              860              ester of dimeric                                                              resin acids  15   172 HDM                                    Polypale                                                                             Hercules  Glycerol ester                                               Ester 10         of polymerized                                                                wood rosin   6    112 HDM                                    Staybelite                                                                           Hercules  Hydrogenated                                                 Resin            wood rosin   165  76 HDM                                     Krumbhaar                                                                            Lawter    Pentaerythritol                                                                            <1   180-190 MM                                 484    Chemicals,                                                                              ester of modi-                                                      Inc., Krum-                                                                             fied wood rosin                                                     bhaar Resin                                                                   Division                                                               Nevehem                                                                              Neville                                                                100    Chemical  +                                                                   Company                                                                ______________________________________                                         * HDM--Hercules Drop Method                                                    MM--Mercury Method                                                            R&B--Ring and Ball                                                      

+A thermoplastic petroleum hydrocarbon resin in which the units in thepolymer are predominantly aromatic or cyclic in structure. It isprepared by the polymerization of unsaturated hydrocarbon fractionsboiling between about 125° and about 250° C, having a Sp. Gr.(15.6/15.6° C) of between 0.90 and 0.95. The polymerizable constituentscomprise between about 30% to 90% by weight and the principalpolymerizable monomers are:

    ______________________________________                                        cyclodiene dimers**    5-30%                                                  indene                 5-20%                                                  vinyl toluene          5-25%                                                  styrene                0-10%                                                  ______________________________________                                         **Such as dicyclopentadiene (C.sub.10); di-methylcyclopentadiene              (C.sub.12) codimer of cyclopentadiene and methylcyclopentadiene               (C.sub.11).                                                              

The balance dry weight of the hydrocarbon fraction is constituted ofessentially unpolymerizable paraffins, napthenes and aromaticscontaining 8 or more carbon atoms per molecule and boiling within theaforementioned range, i.e., between about 125° and 250° C. Theunsaturated hydrocarbon fractions from which the resin is obtained comefrom high temperature and low pressure pyrolysis of normally liquid orgaseous hydrocarbons having 2 or more carbon atoms per molecule. Thecracking operation may be by-products of pyrolytic processes in whichthe principal products sought are low boiling olefines and dienes suchas ethylene, propylene, butenes, butadiene, etc. which are widely usedbase hydrocarbons in the petrochemical and plastics fields includingelastomers. Pyrolysis of both liquid and gaseous hydrocarbons for suchpurposes is well known and need not be described in detail.

    ______________________________________                                                            Nevchem 100                                               Test Property       (Typical Properties)                                      1.  Softening Point (R&B) ° C.                                                                 100                                                   2.  Molecular Weight (No. Ave)                                                                        800                                                   3.  C/H Weight ratio    10.5                                                  4.  Sp. Gr. 25/25° C.                                                                          1.090                                                 5.  Refr. Index 25° C/D                                                                        1.602                                                 6.  Iodine Number       65                                                    7.  Acid Number         <1                                                    List of Test Methods:                                                         1.  ASTM E-28-58-T                                                            2.  Osmotic                                                                   3.  Combustion Analysis                                                       4.  ASTM D-71-52                                                              5.  Neville Method                                                                (toluene solution, extrapolated to solid resin)                           6.  ASTM D-555                                                                ______________________________________                                    

    ______________________________________                                                                       Acid  Softening                                Resin  Manufacturer                                                                             Description  No.   Pt. ° C.                          ______________________________________                                        Foral 85                                                                             Hercules   Fuly hydro-                                                                   genated glycerol                                                              ester of wood                                                                 rosin        9      82 HDM                                  Cellolyn                                                                             Hercules   Internally                                                  104               plasticized                                                                   pentaerythritol                                                               ester of wood                                                                 rosin        30    101 HDM                                  Dymerex                                                                              Hercules   Dimeric resin                                                                 acids        143   152 HDM                                  Pliolite                                                                             Goodyear   Vinyl toluene/                                              VTAC-L            acrylate                                                                      copolymer    6.1    47 R&B                                  Neocryl                                                                              Polyvinyl  Vinyl toluene/                                              B-707  Chemicals  n-butyl metha-                                                                crylate/stearyl                                                               methacrylate                                                                  (disclosed in                                                                 USLP 3,378,513,                                                               Example 23)        115 R&B                                  ______________________________________                                    

All the foregoing fixers except the last two are solvatable in one ormore of the above listed organic solvents; the last two are notsolvatable in most of said solvents but can be employed therewith indisperse form for the first liquid toner.

The third constituent of the first liquid toner is a dispersant whichmay either be solvatable in the solvent system or non-solvatable;conventionally the dispersant is solvatable in said solvent system. Thefunction of the dispersant, as is well known, is to disperse the pigmentparticles of sub-micron range in the non-polar solvent system that isemployed. The dispersant must be compatible with the fixer and desirablyis or includes a fixer in its own right. Desirably, also, the dispersantwill augment the charge direction of the pigment particles.

Examples of solid dispersants having the foregoing physicalcharacteristics are: Lube Oil 564 and FOA 2. Lube Oil 564 ismanufactured by du Pont and is composed of 50% of methacrylate polymerand 50% of kerosene. Insofar as the above examples of dispersants areconcerned, it is the solid constituents that constitutes the dispersant,the liquid carrier merely forming a convenient vehicle therefor. Otherdispersants include: Alkanol DOA manufactured by duPont and constitutingan oil additive constituting a terpolymer prepared from a weight mixtureof 50 parts of octadecenyl methacrylate, 10 parts diethylaminoethylmethacrylate, and 40 parts styrene, the same being polymerized byconventional bulk, solution or dispersion polymerization methodsinvolving known initiators including oxygen-yielding compounds, such asbenzoyl peroxide, and azo compounds such as alpha, alpha'azodiisobutyronitrile. The polymerization process preferably is carriedout in an inert atmosphere, for example, nitrogen or carbon dioxide, atconventional temperatures ranging, as is well known, from 30° to 150° C,depending on the catalyst used, and generally between 50° to 70° C wherethe catalyst is alpha, alpha' azodiisobutyronitrile. The polymerizationis carried substantially to completion to eliminate substantially all ofthe unpolymerized monomers, it being understood that "substantially tocompletion" as used herein denotes that there is a remainder of from 0%to 15% of total monomers. The aforesaid terpolymer is dissolved inkerosene in proportions of 50% by weight of the terpolymer to 50% byweight of kerosene. The terpolymer constitutes, as is seen, severalcompletely organic compounds combined in proportions to effect theoptimum balance between polar-active and oil-soluble groups. The saidterpolymer is large and has an average molecular weight of 50,000.

Still other dispersants that may be used are those disclosed in U.S.Pat. No. 3,048,544, namely alkyl methacrylate maleic anhydride polymer,maleimide polymer, a polymer constituting the reaction product of alkylmethacrylate, polyethylene glycol methacrylate and maleic anhydride, anda polymer constituting the reaction product of alkyl methacrylate,polyethylene glycol methacrylate and imide of maleic anhydride, andtetraethylene pentamine; the polyglycol substituted polyesters disclosedin U.S. Pat. No. 3,083,187; and the polyglycol substituted polyamidesdisclosed in U.S. Pat. No. 3,083,188. The methods of preparation ofthese latter dispersants are detailed in said patents.

The fourth constituent of the first liquid toner is a pigment.

The pigment employed can be any one of the many now known to the art inconnection with liquid electrostatographic developers. As is well-known,these pigments essentially constitute very fine solid particles the sizeof which is in the submicron range, which are opaque in mass and whichare capable of acquiring an electroscopic charge. They are insoluble inthe liquid carrier. So many different kinds and species of pigments areknown that only typical representative examples will be mentioned. Theseare: powdered metals, e.g., powdered aluminum; powdered metal oxides,e.g., powdered magnetic iron oxide; powdered metal salts, e.g., powderedcadmium selenide (CdSe), powdered lead iodide (PbI₂), powdered leadchromate (PbCrO₄); Cyan Blue GT 55-3295 (American Cyanamid Company,Pigments Division)* (74160)** described in United States Letters PatentNo. 2,486,351; Cibacron Black BG (Ciba Company, Inc.); CibacronTurquoise Blue G (Ciba); Cibalon Black BGL (Ciba); Orasol Black BRG(Ciba); Orasol Black RBL (Ciba); Acetamine Blac, CBS (E. I. du Pont deNemours and Company, Inc.); Crocein Scarlet N Ex (du Pont) (27290);Fiber Black VF (duPont) (30235); Luxol Fast Black L (duPont) (Solv.Black 17); Nigrosine Base No. 424 (duPont) (50415 B); Oil Black BG(duPont) (Solv. Black 16); Rotalin Black RM (duPont); Sevron BrilliantRed 3 B (duPont); Basic Black DSC (Dye Specialties, Inc.); HectoleneBlack (Dye Specialties); Azosol Brilliant Blue B (General Aniline andFilm Corporation, Dyestuff and Chemical Division) (Solv. Blue 9); AzosolBrilliant Green BA (General Aniline) (Solv. Green 2); Azosol FastBrilliant Red B (General Aniline); Azosol Fast Orange RA Conc. (GeneralAniline) (Solv. Orange 20); Azosol Fast Yellow GRA Conc. (GeneralAniline) (13900 A); Basic Black KMPA (General Aniline); Benzofix BlackCW-CF (General Aniline) (35435); Cellitazol BNFV Ex Soluble CF (GeneralAniline) (Disp. Black 9); Celliton Fast Blue AF Ex Conc (GeneralAniline) (Disp. Blue 9); Cyper Black IA (General Aniline) (Basic Blk.3); Diamine Black CAP Ex Conc (General Aniline) (30235); Diamond BlackEAN Hi Con. CF (General Aniline) (15710); Diamond Black PBBA Ex (GeneralAniline) (16505); Direct Deep Black EA Ex CF (General Aniline) (30235);Hansa Yellow G (General Aniline) (11680); Indanthrene Black BBK Powd.(General Aniline) (59850); Indocarbon CLGS Conc. CF (General Aniline)(53295); Katigen Deep Black NND Hi Conc. CF (General Aniline) (53190);Nyliton Black B (General Aniline); Palatine Fast Black WANA Conc. CF(General Aniline) (15711); Rapidogen Black 3 G (General Aniline) (AzoicBlk. 4); Sulphon Cyanine Black BA-CF (General Aniline) (26370); ZambeziBlack VD Ex Conc. (General Aniline) (30015); Azo Oil Black (NationalAniline Division of Allied Chemical and Dye Corporation (Solv. Blk. 12);Iosol Blue 6 G (National Aniline) (Solv. Blue 30); Spirit Nigrosine SSB(National Aniline) (50415); Methyl Violet T Lake (N. Y. Color andChemical Co.) (42535); Rubanox Red CP-1495 (The Sherwin-WilliamsCompany) (15630); Victoria Blue Molybdate Lake (Standard Ultramarine andColor Co.) (42595); Black M Toner (General Aniline) a mixture of carbonblack and black dye precipitated on a lake; Toner 8100 (Paul Uhlich andCompany, Inc.) a mixture of carbon black and black dye precipitated on alake; Raven 11 (Columbian Carbon Company) carbon black aggregates with aparticle size of about 25mu, Statex B-12 (Columbian Carbon Co.) afurnace black of 33mu average particle size and chrome green.

The fifth constituent of the first liquid toner is a charge director.

The charge directors which are per se well known in the field of liquidelectrostatographic image developers must be soluble or dispersible inthe paraffinic solvent system and must create or augment anelectrostatic charge on the sub-micron pigment particles. Examples ofuseable charge directors are:

Aerosol OT which is a di-2-ethylhexyl sodium sulfosuccinate;

Aerosol TR which is di-tridecyl sodium sulfoccinate;

the aluminum, chromium, zinc and calcium salts of 3,5-dialkylsalicylicacid, wherein the alkyl group is propyl, isopropyl, butyl, isobutyl,tertiary butyl, amyl, isoamyl and other alkyl groups up to C-18;

the aluminum, chromium, zinc and calcium salts of dialkylgamma-resorcylic acid, wherein the alkyl is as above;

the isopropylamine salt of dodecylbenzene sulfonic acid;

aluminum, vanadium and tin dresinates (the metal dresinates are preparedby adding a solution of the metal sulfate to a solution of the sodiumsalt of Dresinate 731 manufactured by Hercules Powder Co.);

cobalt, iron, lithium, tin and manganese octoates;

OLOA 1200 which is a product of the Oronite Division of CaliforniaChemical Co., the same being a partially imidized polyamine withlubricating-oil soluble polyisobutylene chains and free secondaryamines, its specifications are: gravity at 60° F. API 22.9, specific0.92 flash point by the Cleveland open cup method, 425°, viscosity at210° F., 400 SSU, color (ASTM D-1500) L55D, nitrogen, percentage byweight 2.0, and alkalinity value, (SM-205-15) 43;

soya bean lecithin;

an aluminum salt of 50-50 by weight mixture of the mono- anddi-2-ethylhexyl esters of pnosphoric acid;

zinc, lead, copper, cadmium, calcium, aluminum and iron stearates;

zinc and aluminum palmitates;

aluminum oleate;

copper, manganese, cobalt and lead linoleates;

manganese linoresinate; and

Nalcamine G-14, manufactured by Nalco Chemical Co., this being1-[2-hydroxyethyl]-2-[mixed pentadecyl and heptadecyl]-2-imidazoline.

The linoresinates are metal soaps of tall oil.

The various constituents of the first liquid toner are almost invariablychemically inert to one another at ambient temperatures and are inert tothe various constituents of the second liquid toner at liketemperatures. All of the constituents of the first liquid toner areselected and admixed solely for their physical characteristics andgenerally not for chemical interaction. The constituents are heat stableunder conditions of use and at temperatures to which they are exposed intransit and in storage. An electrostatographic developing bath solelyconstituting the first liquid toner will not gel under the operatingconditions prevailing in a liquid electrostatographic developingapparatus, i.e. at a temperature up to as high as 125° F. Moreover, suchheat stability and non-gelling characteristics carry over into thesecond liquid developer component of the hybrid liquid developer of thepresent invention.

The following are examples of liquid electrostatographic first toners inconcentrated form:

                  EXAMPLE I                                                       ______________________________________                                        40        gs.        Krumbhaar 484                                            15        gs.        Toner 8100                                               15        gs.        Spirit Nigrosine SSB                                     5         gs.        Raven 11                                                 50        gs.        Alkanol DOA                                              150       mls.       Shell Sol 71                                             2         gs.        Manganese linoleate                                      2         gs.        Aluminum stearate                                        ______________________________________                                    

                  EXAMPLE II                                                      ______________________________________                                        25        gs.        Nevchem 100                                              9         gs.        Toner 8100                                               9         gs.        Spirit Nigrosine SSB                                     120       gs.        Shell Sol 71                                             0.25      g.         Aluminum dresinate                                       17.5      gs.        Alkanol DOA                                              ______________________________________                                    

                  EXAMPLE III                                                     ______________________________________                                        55        gs.        Resin NC-11                                              17.5      gs.        Alkanol DOA                                              182       gs.        Shell Sol 71                                             0.5       g.         Aluminum stearate                                        28        gs.        Cyan Blue GT 55-3295                                     ______________________________________                                    

                  EXAMPLE IV                                                      ______________________________________                                        25        gs.        Staybelite                                               20        gs.        Alkanol DOA                                              10        gs.        Mineral oil (U.S.P.)                                     15        gs.        Toner 8100                                               9         gs.        Statex B-12                                              100       gs.        Isopar K                                                 1         g.         Tin octoate                                              ______________________________________                                    

The mineral oil is employed to slightly increase viscosity and therebyreduce the settling for insoluble constituents and to inhibit thetendency of the concentrate to dry out and form a crust in the feedervalve.

                  EXAMPLE V                                                       ______________________________________                                        55        gs.        Resin NC-11                                              17.5      gs.        Lube Oil 564                                             1         g.         Aluminum stearate                                        182       gs.        Isopar H                                                 30        gs.        Powdered cadmium selenide                                ______________________________________                                    

                  EXAMPLE VI                                                      ______________________________________                                        25    gs.    Nevchem 100                                                      20    gs.    Alkanol DOA                                                      10    gs.    Polymerized castor oil                                           15    gs.    Black M Toner                                                    9     gs.    Statex B-12                                                      100   gs.    Isopar K                                                         0.5   g.     Cobalt octoate (12% solution in mineral oil                      ______________________________________                                    

The polymerized castor oil is used for the same purpose as the mineraloil.

                  EXAMPLE VII                                                     ______________________________________                                        25        gs.        Foral 85                                                 20        gs.        Alkanol DOA                                              10        gs.        Polymerized castor oil                                   15        gs.        Toner 8100                                               9         gs.        Statex B-12                                              100       gs.        Isopar G                                                 0.5       g.         Aluminum stearate                                        ______________________________________                                    

                  EXAMPLE VIII                                                    ______________________________________                                        25    gs.    Nevchem 100                                                      20    gs.    Alkanol DOA                                                      10    gs.    Polymerized castor oil                                           15    gs.    Toner 8100                                                       9     gs.    Statex B-12                                                      100   gs.    Isopar K                                                         0.5   g.     Cobalt Octoate (12% solution in mineral oil)                     ______________________________________                                    

                  EXAMPLE IX                                                      ______________________________________                                        25     gs.      Staybelite Resin                                              20     gs.      Alkanol DOA                                                   10     gs.      Polymerized castor oil                                        15     gs.      Toner 8100                                                    9      gs.      Statex B-12                                                   100    gs.      Isopar G                                                      5      drops    Aluminum dresinate (10% solution in                                           Isopar G)                                                     ______________________________________                                    

                  EXAMPLE X                                                       ______________________________________                                        25        gs.        Staybelite Resin                                         20        gs.        Alkanol DOA                                              10        gs.        Polymerized castor oil                                   20        gs.        Statex B-12                                              4         gs.        Cyan Blue GT                                             1         g.         Aluminum stearate                                        100       gs.        Isopar K                                                 ______________________________________                                    

Each of the foregoing concentrated liquid electrostatographic developersis formed by introducing all of the recited ingredients into a ball milland milling the same therein at room temperature or above, e.g. 110° F,for an extended period of time, e.g. 24 hours.

The second liquid toner used in the hybrid toner of the presentinvention is described in detail in application Ser. Nos. 810,841 and7,253, but is redescribed below for the sake of completeness. The secondliquid toner essentially consists of a solvent system, optionally acoloring agent, and a complex molecule including plural polymericmoieties of which at least one is solvated by the solvent system and atleast one is non-solvated by the solvent system, the color agentoptionally being in the form of a moiety of the molecule in the natureof a chromophore. At least one of the polymeric moieties is of aresinous nature and serves as a fixative. The nonsolvated polymericmoiety provides a solid particle in the solvent system (the continuousphase) enabling the desired size of particles 25 mμ and 25μm to beformed and permitting electrophoretic deposition to take place in theformation of a patterned deposit on a substrate, e.g., enablingelectrostatic attraction to take place between a particle and a latentelectrostatic image on a copy sheet. The solvated polymeric moietyfunctions to maintain the complex molecule in suspension, that is tosay, to prevent settling of the molecule and hence, in effect, operatesas a dispersing agent. Thus, in the complex molecule, several functionsof constituents of conventional (first type) toners are amalgamated. Itshould be observed that the polymeric moiety or moieties which impartthe resinous characteristic to the complex molecule may be either thesolvent solvated polymeric moiety or the solvent non-solvated polymericmoiety or both. This complex molecule is a so-called "tailored"molecule, that is to say, it is an artifically created molecule which ina single compound provides plural functions required in a toner of thefirst type the presence of plural chemically separate constituents. Acharge director is an additional most desirable component of the secondliquid toner.

The basic building block of the second liquid toner is the solventsystem. The term "basic building block" is not used in the sense thatthe solvent system is the core of the complex molecule which isemployed, but rather that the nature of the solvent system influencesthe particular type complex molecule that is to be employed. Once thesolvent system has been chosen, certain parameters of the second liquidtoner developer constituents and specifically of the complex molecule,are indicated. Any type of solvent system can be used which iscompatible with the first liquid toner, indeed the two liquid toners aremutually compatible, and with the particular apparatus and method usingany specific form of a hybrid liquid toner embodying the presentinvention. Preferably both the first and the second liquid toners employthe same solvent system. Both liquid toners of the two toners whoseadmixture constitutes the present invention preferably are based upon anon-polar solvent system such as is conventionally employed presently inthe creation of most patterned deposits and is currently widely used inelectrostatographic toners. Nevertheless, the second liquid toner is notlimited to a non-polar solvent system and can be equally well employedwith a polar solvent system, where such a system is practical in anyspecific apparatus or method that can make use of such a toner and wherethe first liquid toner uses the same or a compatible solvent system.Because the present large-scale commercial use of liquid toners is withapparatuses and methods that utilize non-polar solvents, the followingdescription of the second liquid as to the particular examples andcompositions stresses a non-polar continuous phase, i.e., solventsystem. Such a non-polar solvent system includes an organic non-polarliquid having the characteristics of those previously mentioned aboveand referred to in particular under subdivisions (a)-(h) above which areincorporated here by reference. Examples of such solvent systems areidentical to those described with respect to the solvent systems of thefirst liquid toner and, indeed, it is preferred to use identical solventsystems for both the first and the second liquid toners so that thehybrid toner utilizes a single solvent system.

The second liquid toner uses with the solvent system a complex moleculehaving the polymeric moieties mentioned above. Hence, the second liquidtoner is basically a latex toner, which is to say, a toner that lookslike a natural latex in that it constitutes a liquid continuous phasehaving the desired attributes for use in a patterned deposition system,together with a dispersed phase which is an amphipathic polymer. Theterm "latex" as used herein refers to a colloidal suspension of asynthetic polymer in any liquid, for instance, as prepared by emulsionor suspension polymerization. An "amphipathic" substance is one that hasan affinity for two different materials, for instance, oil or water, ortwo different phases, so that one polymeric moiety of the amphipathicpolymer, which is the foregoing complex molecule, will be solvated bythe phase for which it has an affinity, which, in this instance, is thesolvent system, and another polymeric moiety will not be solvated bythis same phase, that is to say, will be insoluble in this phase, sothat the phenomenon is created when the amphipathic polymer is containedin the solvent system of at least one polymeric moiety of the polymerbeing solvated by the solvent system and at least one polymeric moietybeing non-solvated by the solvent system. The amphipathic polymercombines in one complex molecule the fixing agent, which is one or moreof the polymeric moieties, the dispersing agent, which is one or more ofthe polymeric moieties, and optionally, a color agent, which is one ormore of the polymeric moieties. This complex molecule, i.e., amphipathicpolymer, by virtue of the fact that it is a molecule rather than acomposition including a mixture of pigment particles, creates a narrowrange of size distribution of the non-solvated particles whichultimately are deposited on a substrate, e.g., a copy sheet, as byelectrostatographic development, to create a patterned deposition.Desirably the particle size distribution of the non-solvated particlesin the second liquid toner is within two orders of magnitude andpreferably is within about one order of magnitude. The foregoing rangesare what is denoted by the term "mono-dispersed".

The second liquid toner is created generally as follows: Firstly, thesolvent system for the second toner is chosen, for example, a non-polarsolvent such as a petroleum fraction like the ones mentioned above,although as previously observed, other solvents could be used, e.g.polar solvents such as water.

It is appropriate to reiterate at this point that patterned depositionsutilizing electrostatic phenomena, e.g., electrophoresis, do notnecessarily involve the use of non-polar solvent systems for either ofthe first and the second liquid toners. Thus an electrostatic methodusing water as the carrier system in electrostatography is shown in U.S.Pat. No. 3,425,829, issued Feb. 4, 1969. Other suitable solvent systems,by way of example, i.e., solvent systems other than petroleum fractionsand water, include alcohols, e.g., those having 1 to 6 carbon atoms,such as ethylene glycol; ethers, including ethyl isobutyl ether, methylisopropyl ether, the (C₁ -C₄) alkyl mono ethers of ethylene glycol, anddioxane; ketones, including acetone, methyl ethyl ketone, methylisopropyl ketone, and ethyl isobutyl ketones; esters, including ethylacetate, amyl acetate, butyl propionate, and the acetates of the mono-(C₁ -C₄)- alkyl ethers of ethylene glycol; and halogenated hydrocarbons,such as chloroform, ethylene dichloride, monochloro benzene and certainFreons.

After selection of the solvent system a polymeric backbone molecule ischosen for the second liquid toner, which is solvated by the selectedsolvent system, i.e, which is fully soluble to the limit of itssolubility. Next a graft or block polymerization or copolymerization iscarried out in such a manner, hereinafter described, that non-solvatedpolymeric chains, which is to say, polymeric chains which are notsolvated by the chosen solvent system, are created in the solvent systemand are chemically joined with, i.e., to, the solvated polymericbackbone molecule. The mechanism by which the chains are created andchemically joined is not of critical importance. For example, the chainsfirst can be formed and then grafted onto the polymeric backbonemolecule or a molecule of a grafting monomer can be first reacted withthe polymeric backbone molecule and subsequently this first monomer canbe polymerized with the other grafting monomers present in the solventsystem.

The non-solvated polymeric moiety, i.e., fraction or chains, originatesas a monomer which usually and preferably is solvated by the solventsystem for convenience in carrying out the reaction and to minimize thetime required for the reaction and also to eliminate the need forsolubilizers or multi-solvent systems in the second liquid toner.However, as the reaction for the formation of the chains proceeds, theaddition to the backbone polymer, which is to say, the newly formedchains, become progressively non-solvated and eventually becomes anon-solvated polymeric moiety (portion) which constitutes a dispersedphase, this, despite the fact that the polymeric backbone still issolvated by the solvent system. It is interesting to observe that thereaction as it takes place initially causes a transformation of theclear solution of the solvated backbone polymer and of the solvatedmonomer first into a slightly hazy stage and then becomes more turbid asthe minutes pass until ultimately a latex is formed.

It is also possible to use a reverse process in which a non-solvatedpolymeric backbone is partially solvated by graft or blockpolymerization.

As mentioned previously, the largest present-day commercial use forliquid toners is in electrostatography such as is used in the so-called"liquid" xerographic copying machines. The solvent system used in liquidtoners for such purpose is usually a petroleum fraction such asdescribed heretofore with respect to the first liquid toner and, hence,in detailing various process steps in the manufacture of the complexmolecule this particular solvent system will be employed, although it isunderstood that the second liquid toners can employ any solvent systemwhatsoever.

Assuming, then, that the solvent system for the second liquid toner is apetroleum fraction, a polymeric backbone material is selected which issolvated by such petroleum fraction. A popularly employed petroleumfraction is odorless mineral spirits (hereinafter OMS). There are manypolymeric materials which are solvated by OMS. These include, e.g.,polymeric materials derived from natural sources such as crepe rubber;refined oxidized linseed oil and degraded rubber, and synthetic polymerssuch as alkyd resins; polyisobutylene; polybutadiene; polyisoprene;polyisobornyl methacrylate; acrylic polymers of long chain esters ofacrylic or methacrylic acid such as stearyl, lauryl, isodecyl, octyl,2-ethylhexyl and hexyl; butyl esters of acrylic or methacrylic acids;polymeric vinyl esters of long chain acids such as vinyl stearate, vinyllaurate, vinyl palmitate and vinyl myristate; polymeric vinyl alkylethers, including poly (vinyl ethyl ether) sold under the trademarkBakelite EDBM by Union Carbide Corp., poly (vinyl isopropyl ether), poly(vinyl isobutyl ether) and poly (vinyl n-butyl ether). As can be seenfrom the examples given, the polymers chosen have a structure similar tothat of the solvent which is going to solvate them, i.e., the polymersand the solvent system have a similar degree of polarity. As long asthis similar polarity is maintained, copolymers, e.g., laurylmethacrylate-butyl acrylate, t-octyl methacrylate-butyl methacrylate,lauryl methacrylate-glycidyl methacrylate, 2-ethyl hexylacrylate-acrylic acid, isodecyl methacrylate-diethylaminoethylmethacrylate and vinyl toluene-butadiene; terpolymers, e.g., laurylmethacrylate-isodecyl methacrylatemethyl methacrylate, stearylmethacrylate-cyclohexyl acrylatemethacrylic acid, octylacrylate-crotonic acid-dodecyl methacrylate, glycidylmethacrylate-stearyl methacrylate-lauryl methacrylate, laurylmethacrylate-octyl methacrylate-glycidyl methacrylate and isodecylmethacrylate-stearyl methacrylate-acrylic acid; and tetrapolymers, e.g.,N-vinyl pyrrolidone-butyl acrylate-lauryl methacrylate-stearylmethacrylate and acrylic acid-stearyl acrylate-methylmethacrylate-isodecyl acrylate, may be used, as well as block and graftcopolymers, block and graft terpolymers, block and graft tetrapolymersand multi-type monomer/polymers in general as the backbone structure.

If desired, the backbone structure with or without added chains can becreated in a solvent other than that in which it is ultimately to beused, i.e., in a solvent other than the solvent system of the secondliquid toner. The original solvent in which the backbone structure withor without added chains is created can either be extracted or it can bepart of a multi-solvent system in the second liquid toner. Many monomerswhich it might be desirable to employ in building a backbone structureare not sufficiently solvated by OMS or other solvent system of thesecond liquid toner to enable the polymerization of the desiredstructure to be effected in OMS. In such a case, a copolymerizationutilizing such insufficiently solvated monomers may be carried out in asolvent of higher K.B. number with another monomer which is solvated byOMS, as long as the resultant copolymer contains enough of the secondmonomer so that the backbone can be solvated by OMS. Such acopolymerization, for example, could be carried out in benzene, theresulting copolymer precipitated by the addition of methanol, freed fromsolvent, and dissolved in OMS to function as the backbone during thesubsequent graft or block polymerization or graft or blockcopolymerization.

The discussion above of synthetic polymeric materials suitable for useas the backbone, also often hereinafter sometimes referred to as the"precursor", in an OMS-based electrostatographic toner system is notlimited to addition polymers; synthetic condensation polymers can alsoserve as the backbone or precursor in this system as long as they can besolvated by the chosen solvent medium, e.g., the self-condensationpolymer of 12-hydroxystearic acid.

Inasmuch as the second liquid toner is not limited to the use of anyparticular solvent system, there is no limitation on the monomers thatcan be used to fabricate the polymeric constituents of such system. Inthe particular system being discussed, however, that based on OMS, thefollowing list of backbone polymers is exemplificative but notexclusive:

(a) the homopolymers of the C₄ -C₂₂ esters of acrylic and methacrylicacid, such as polyhexyl methacrylate and acrylate, polyisodecylmethacrylate and acrylate, polylauryl methacrylate and acrylate,polytetradecyl methacrylate and acrylate, and polystearyl methacrylateand acrylate, all in the molecular weight range of about 10³ to about10⁶, but preferably not smaller than 10⁴ ;

(b) copolymers, with each other, of any of the above monomers used toform the homopolymers under (a), and also with the methyl, ethyl,isopropyl and propyl esters of acrylic and methacrylic acid, providedthat the ratios of non-solvated to solvated monomers are kept in aproportion such as to insure solvation of the resulting copolymer byOMS;

(c) copolymers of the above mentioned methacrylic and acrylic acidesters with monomers containing other functional groups as, for example,acrylic acid, methacrylic acid, crotonic acid, maleic acid, atropicacid, fumaric acid, itaconic acid, citraconic acid, acrylic anhydride,methacrylic anhydride, maleic anhydride, acryloyl chloride, methacryloylchloride, acrylonitrile, methacrylonitrile, acrylamide and derivativesthereof, methacrylamide and derivatives thereof, hydroxyethylmethacrylate and acrylate, hydroxypropyl methacrylate and acrylate,dimethylaminomethyl methacrylate and acrylate, dimethylaminoethylmethacrylate and acrylate, diethylaminomethyl methacrylate and acrylate,diethylaminoethyl methacrylate and acrylate, t-butylaminoethylmethacrylate and acrylate, allyl alcohol and derivatives thereof,cinnamic acid and derivatives thereof, styrene and derivatives thereof,methallyl alcohol and derivatives thereof, propargyl alcohol andderivatives thereof, indene and derivatives thereof, norbornene andderivatives thereof, vinyl ethers, vinyl esters and other vinylderivatives, glycidyl methacrylate and acrylate, mono- and dimethylmaleate, mono- and diethyl maleate, mono-n-butyl maleate, mono-sec-butylmaleate, mono-ter-butyl maleate, monobenzyl maleate, mono-2-ethylhexylmaleate, mono-n-octyl maleate, mono- and dimethyl fumarate and mono- anddiethyl fumarate;

(d) homopolymers of olefins such as butadiene, isoprene and isobutylene,and copolymers of these monomers with any of the monomers listed aboveconsistent with the solvation limitation as described under (b);

(e) terpolymers and tetrapolymers of the above;

(f) polycarbonates, polyamides, polyurethanes and epoxies.

With the backbone, i.e., precursor, chosen, there are added on to thisbackbone polymeric chains of a different degree of polarity from that ofthe solvent so that these chains although grafted on or blockpolymerized to the solvated backbone, will themselves be non-solvated bythe solvent system and, hence, form a dispersed phase. This addition ofsuch chains is carried out via either a block or graft polymerization asjust noted. Suitable monomers which form polymers that are too polar tobe solvated by the OMS solvent medium are vinyl acetate, methyl acrylateand methacrylate, ethyl acrylate and methacrylate, propyl acrylate andmethacrylate, isopropyl acrylate and methacrylate, hydroxy ethylacrylate and methacrylate, hydroxy propyl acrylate and methacrylate,acrylonitrile, methacrylonitrile, acrylamide, methacrylamide, acrylicacid and anhydride, methacrylic acid and anhydride, mono methyl maleate,mono ethyl maleate, mono-n-butyl maleate, mono-sec-butyl maleate,mono-ter-butyl maleate, monobenzyl maleate, mono-2ethylhexyl maleate,mono-n-octyl maleate, mono methyl fumarate, mono ethyl fumarate,styrene, vinyl toluene, maleic acid and anhydride and crotonic acid andits anhydride. The invention is not limited to homopolymers in thisfurther polymerization procedure; copolymers and terpolymers or polymersof greater degrees of complexity, but of the proper polarity, could bejoined to the chosen solvated backbone structure to form the latex.

When a grafting procedure is chosen for the latex forming step, andthere are no ethylenic or other unsaturated bonds available in thebackbone for accepting the graft, polymeric chains can be grafted onto asaturated backbone, nevertheless, through the use of activating methodsknown to those skilled in the art. This method, however, althoughuseful, leads to a haphazard activation by the initiator employed of asite or sites in the backbone molecule which subsequently serve toinitiate the polymerization of the grafting monomer. A preferred method,rather than haphazard activation, is to construct the backbone moleculeof the second liquid toner in such a way as to produce ethylenicallyunsaturated double bonds or other unsaturated bonds containing pendantmoieties to serve as sites to be activated by the initiator for in situgraft polymerization. Thus, there may be employed an OMS solvatedbackbone molecule consisting of a copolymer of stearylmathacrylate-glycidyl methacrylate of the proper (27:1) monomer ratioand molecular weight, e.g., 10,000 to 150,000. Methacrylic acid can bereacted with this polymer in the presence of a polymerization inhibitorto provide ethylenically unsaturated double bond containing sitesthrough an esterification reaction for activation and subsequent in situpolymerization or copolymerization. In such a manner, precursors for agraft polymerization or copolymerization can be made. The term"precursor" as used herein denotes a backbone such as described, as wellas a treated (activated) backbone, which is to be used as the base forreaction to form a latex.

Many different reactions can be utilized to introduce theseethylenically unsaturated double bond containing pendant groups into theprecursor. If the monomer used in the backbone chain is called Monomer 1(said monomer is at least one of two monomers which forms the backbonechain and which is present in a minority proportion by weight and whichincludes an unsaturated bond before copolymerization, said bond havingbeen reacted in the formation of the copolymer but still contains areactive group) and the additional monomer used to form the precursor iscalled Monomer 2 (the latter monomer is specifically selected to bereactive with the reactive group of Monomer 1), the following areillustrative examples:

    ______________________________________                                        Monomer 1         Monomer 2                                                   ______________________________________                                                              Acrylic acid                                                                  Methacrylic acid                                        Glycidyl methacrylate Maleic acid                                              or acrylate   --     Fumaric acid                                                                  Atropic acid                                                                  Allylamine                                                                    Vinyl amine                                                                   Hydroxyethyl methacrylate                                                     and acrylate                                                                  Hydroxypropyl methacrylate                              Acryloyl or methacryloyl                                                                            and acrylate                                             chloride      --     Acrylamide                                                                    Methacrylamide                                                                Allyl alcohol                                                                 Allylamine                                                                    Vinyl amine                                             Acrylic acid          Vinyl pyridines                                         Methacrylic acid      Glycidyl methacrylate                                   Maleic acid    --     Vinylamine                                              Crotonic acid         Allylamine                                              Alkyl hydrogen maleates                                                                             Dialkylaminoalkyl meth-                                 Aryl hydrogen maleates                                                                               acrylates and                                          Alkyl hydrogen fumarates                                                                             acrylates                                                                    Allylamine                                              Vinyl isocyanate                                                                             --     Vinylamine                                                                    Methacrylyl acetone                                     Cyanomethylacrylate                                                                          --     Vinylamine                                                                    Allylamine                                                                    Allylamine                                              Vinyl β-chloroethyl-                                                                    --     Vinylamine                                               sulphone             Allyl alcohol                                                                 Hydroxyalkyl methacrylates                                                    Glycidyl methacrylate                                   Methacrylic anhydride Vinylamine                                              Acrylic anhydride                                                                            --     Allylamine                                              Maleic anhydride      Hydroxyalkyl methacrylates                                                    Allyl alcohol                                                                 N-hydroxymethyl                                         Vinyl sulphonic acid                                                                         --      methacrylamides                                        Vinyl phosphoric acid Alkoxymethyl                                                                   methacrylamides                                        ______________________________________                                    

The reverse reactions can also be utilized, i.e. Monomer 2 can becopolymerized into the backbone and subsequently condensed with Monomer1 to create the precursor.

With the precursor formed, the latex is prepared by carrying out, in aliquid system wherein the precursor or additional fraction (polymericmoiety) is fully solvated and the other fraction (polymeric moiety) notfully solvated, the polymerization of the monomer or comonomers chosenfor the additional fraction which preferably is the dispersed phase inthe presence of and in conjunction with the precursor. In the preferredform of the second liquid toner, the monomer or monomers chosenpolymerize to a material which is nonsolvated by the solvent systememployed in the second liquid toner. For example, in an OMS-based systemusing the stearyl methacrylate-glycidyl methacrylate-methacrylic acidprecursor, typical useful monomers for the additional fraction includemethyl methacrylate, methyl acrylate, ethyl methacrylate, ethylacrylate, isopropyl methacrylate, styrene, vinyl acetate, vinylchloride, vinyl toluene, acrylonitrile and methacrylonitrile, ashomopolymers or copolymers, or any one or more of the above with maleicanhydride, crotonic acid, acrylic acid, mono methyl maleate, mono ethylmaleate, mono-n-butyl maleate, mono-sec-butyl maleate, mono-ter-butylmaleate, monobenzyl maleate, mono-2-ethylhexyl maleate, mono-n-octylmaleate, mono methyl fumarate, mono ethyl fumarate, methacrylic acid,dimethylaminomethyl methacrylate, or terpolymers or tetrapolymers of anyof the foregoing. When this polymerization is carried out, part of themonomer polymerizes with the precursor molecule (solvated backbone) toform a graft copolymer which is one form of complex tailored moleculefor the second liquid toner, and this serves to stabilize any dispersepolymer particles which are not grafted.

It will be appreciated that the dispersed phase which, in principle, isthe non-solvated moiety of the complex amphipathic resin molecule, alsomay include dispersed non-grafted nonsolvated polymer particles.Although the latter are not particularly desirable by virtue of theirnon-solvation, they are aggregatable and, moreover, are able to behaveelectrophoretically so that they are capable of being selectivelyattracted to differentially electrostatically charged areas, whereby toform a graphic representation by electrostatography.

With a latex of the foregoing character constituting the complextailored amphipathic resin molecule as thus far described, the fixative(substrate bonding) and dispersant functions are combined into a singlemolecule which will behave properly in an electrostatographic system.That is to say, this molecule, of which there are a great number in anyparticular second liquid toner, will be capable of charge direction andfixation and yet will not, because of the solvated moiety, tend tosettle so that it has a "built-in" dispersing ability.

This complex tailored molecule, together with the solvent system, iscapable, by itself, in conjunction with a charge director, of use as asecond liquid toner because it need not form a visible selectivedeposition on a differentially electrostatically charged substrate, e.g.when used to deposit an image that will be used as a lithographicmaster. However, it is additionally desirable for the second liquidtoner to contain a color ranging from black to white through all of thevarious hues. Phrased differently, it is desirable to color thesuspended latex particles to that when they are preferentially attractedto differentially electrostatically charged regions of a substrate anddeposited thereon, the films left by the deposit ("film" is here used ina sense not of a broad continuous layer but, rather, of a coating whichmay cover only a physically small portion of an area and may have anytype of peripheral configuration depending upon the image that is to beproduced) will likewise be colored so that they can be readily visibleand also, if desired, so that a specific color can be created.

One way of imparting the color is by using either pigments or dyes addedto the latex and physically dispersing them therein as by ball millingor high shear mixing.

The pigment employed in the second liquid toner can be any one of themany now known to the art in connection with liquid electrostatographicdevelopers. As is well known, these pigments essentially constitute veryfine solid particles the size of which is in the submicron range andwhich are opaque en masse. They are insoluble in the liquid system.Typical pigments are those listed hereinabove with respect to the firstliquid toner.

When the dispersed phase is colored by pigment, such preferably arenon-reactive with the amphipathic polymer of the second toner and withthe constituents of the first liquid toner. It is believed that pigmentparticles are held to the non-solvated latex polymeric moiety by secondorder forces only, i.e., are thus held to the dispersed phase of thecomplex amphipathic resin molecule.

In another form of the second liquid toner pigments or dyes are employedwhich are chemically bonded to the latex, that is to say, which becomechemically bonded to and are part of the complex molecule. The chemicalbonding can be to the precursor before the graft or block polymerizationof the added chains or it can be to the chains added by graft or blockpolymerization.

As to the dyes, as distinguished from pigments, these may be used tocolor the specific complex amphipathic resin polymer molecule of thesecond liquid toner and specifically to color the dispersed non-solvatedphase thereof by being held thereto by second order or surfaceadsorption forces or the dyes can be chemically reacted with the complextailored molecule, either after its formation, or to the precursor, orto the chain as it is being or after it has been grafted or blockpolymerized.

The dyes are incorporated in the second liquid toner by second order orsurface adsorption forces, as by heating the latex and dye together fora sufficient time, for example, one to twelve hours. One type of exampleof such dyes is disperse dyes for dyeing polyester and copolymers ofacrylonitrile and vinyl chloride where the dispersed phase is apolyester or a copolymer of acrylonitrile and vinyl chloride. Such dyesinclude: Latyl Orange 3R (DuPont) (C.I. Disperse Orange 26); CalcosperseYellow GL (American Cyanamid) (C.I. Disperse Yellow 57); CalcosperseBlue B (American Cyanamid) (C.I. Disperse Blue 77); Foron Blue BGL(Sandoz Inc.) (C.I. Disperse Blue 73); Latyl Brown MS (DuPont) (C.I.Disperse Brown 2); and Latyl Violet BN (DuPont) (C.I. Violet 27). Otherexamples of such dyes are basic dyes for polyacrylics, where thedispersed phase is a polyacrylic. Typical of such dyes are: Sevron BlueBGL (Dupont) (C.I. Basic Violet 15); Deorlene Brilliant Red 3B (Ciba)(C.I. Basic Red 26); Calcozine Acrylic Blue G (American Cyanamid) (C.I.Basic Blue 38); Astrazon Yellow Brown GGL (Farbenfabriken Bayer) (C.I.Basic Orange 30); and Astrazon Red 5BL (Farbenfabriken Bayer) (C.I.Basic Red 24).

A better approach and one which is preferred in a more sophisticatedform of the second liquid toner is to create a dispersed (non-solvated)phase of a copolymer containing reactive groups which will react withreactive groups of a chromophoric nature, for example, a dispersed phaseof a copolymer containing basic groups which can be reacted with aciddyes. An example of a dispersed phase of a latex which can be used inthe foregoing manner is a terpolymer of acrylonitrile, 2-methyl-5-vinylpyridine and vinyl acetate. Such terpolymer can be reaction dyed withdyes containing acid groups of which examples are: Pontacyl BrilliantBlue A (DuPont) (C.I. Acid Blue 7); Calcocid Brilliant Blue FFR(American Cyanamid) (C.I. Acid Blue 104); Femazo Brown N (GeneralAniline) (C.I. Acid Brown 14); Crocein Scarlet N (DuPont) (C.I. Red 73);Oxanal Yellow I (Ciba) (C.I. Acid Yellow 63); and Benzyl Black 4BN(Ciba) (C.I. Black 26A).

Such a complex tailored molecule is tri-functional. It contains not onlythe dispersant and fixative functions but also the coloring functions.Such a second liquid toner has an essentially mono-dispersed phase,i.e., a small range of variation of particle size.

An alternate method of creating the more sophisticated complextri-functional amphipathic resin molecule which embodies the aforesaidthree functions of fixing, dispersing and coloring is to create adispersed phase of a copolymer containing acid groups which then arereacted with basic dyes (instead of with the aforesaid acid dyes). Anexample of a dispersed phase of such a latex is a copolymer of vinylacetate-maleic acid. This is dyeable with dyes containing basic groupsof which examples are: Magenta (C.I. Solvent Red 41, C.I. No. 42510B),Crystal Violet (C.I. Solvent Violet 9, C.I. No. 42555B), Bismarck Brown(C.I. Solvent Brown 12, C.I. No. 21010B, Victoria Blue BA (C.I. SolventBlue 4, C.I. No. 44045B), Victoria Blue R (C.I. Solvent Blue 6, C.I. No.44040R), Victoria Blue 4R (C.I. Solvent Blue 2, C.I. No. 43563B),Copying Black SK (C.I. No. 11975), Janus Green B (C.I. No. 11050),Auramine O (C.I. Solvent Yellow 34, C.I. No. 41000B), Victoria Green(C.I. Solvent Green 1, C.I. No. 42000B), and Rhodamine (C.I. Solvent Red49, C.I. No. 45170B).

Still another method of creating a tri-functional complex tailoredamphipathic resin molecule for the second liquid toner by virtue of achemical reaction for bonding the color agent to the block or graftmodified precursor is to create a dispersed phase of a copolymercontaining electron acceptor groups, for example, maleic acid orcrotonic acid which are Lewis acids and which are then reacted withcolor precursors that are well known to the art. An example of thislatter tri-functional sophisticated complex molecule is a terpolymer ofmaleic anhydride-vinyl acetate-styrene (on a solvated backbone) andreacted with a color precursor such for instance as bis(p-dimethylaminophenyl)-benzotriazyl methane. A second liquid tonerembodying the foregoing complex molecule will, per se, produce a deepblue colored deposit.

Where the pigment or dye is reacted with the added groups in thedispersed phase, the amount of pigment employed can fluctuate from aslow as 5% to a theoretical 100% of the calculated stoichiometric amountin the second liquid toner. Nevertheless, it is preferred to have theamount of dye or pigment thus incorporated vary between about 10% and50% of the stoichiometric amount, with best results having been obtainedat about 25% of the stoichiometric figure.

There is yet another way for coloring latexes of the second liquidtoners. This is to color the precursor itself, which is to say, thebackbone that is the solvated phase rather than to color the dispersedunsolvated phase. Although there could be used for coloring theprecursor some of the methods recited above to color the dispersed phaseby chemical reaction or by second order bonds or surface adsorption oreven by chemical reactions of color agents with the precursor, a highlypreferred method is to employ a dye which is copolymerized into theprecursor itself, that is to say, the solvated backbone, before thebackbone is grafted or block polymerized with the non-solvated moieties(chains). An example of such a process is set forth below (EXAMPLEXVIII) along with many other examples of methods of manufacturing thecomplex amphipathic resin molecule of the second liquid toner.

It should be observed, moreover, that, if desired, both the dispersedphase and the solvated precursor can be dyed by any of the manners abovediscussed in detail.

As thus far described, there has been provided a stable latex whichconstitutes practically all of the necessary ingredients of the secondliquid toner, these including the liquid solvent system with the complexamphipathic resin molecule having solvated and non-solvated polymericmoieties and which is tri-functional as to the fixative, dispersant andcolorant or includes a separate (non-reacted) color agent. It still is,nevertheless, extremely desirable to include in the second liquid tonera charge director or directors, the same adding greatly to the depth ofcolor obtained and aiding in contrast. Hence, there preferably isincluded in the second liquid toner as a constituent over and above thesolvent system, the complex molecule and a separate colorant, if one isnot included as a moiety of the complex molecule, a charge director in auseful concentration. In electrostatographic development a chargedirector present in a suitable concentration is to all intents andpurposes a necessity. The charge director or directors chosen for thesecond liquid toners may be any of those mentioned with respect to thefirst liquid toner and, indeed, the same charge director or directorsare preferably used for both the first and the second liquid tonerswhich are mixed to form the hybrid liquid toner or the presentinvention.

The amounts of the different non-carrier constituents of the first andthe second liquid toners are capable of extremely wide variation,indeed, so wide that assigning specific figures thereto of the extremeranges which function satisfactorily in the hybrid toner is largelymeaningless. For example, the amounts will vary with the type ofmachine, climate, machine speeds, types of paper and experience of theoperator, to mention but a few. Also, particularly in the case of thecoloring material, the amounts will vary with the intensity of the dyeor pigment and the desired degree of intensity of the image. Generallyspeaking, moreover, the amounts of the individual non-carrierconstituents will increase or decrease together, although not in strictproportion. Bearing all of this in mind and in order to assist workersin the art in the preparation of hybrid toners embodying the presentinvention, the following represent approximately maximum and minimumamounts of the various non-carrier constituents per liter of the firstand second liquid toners in a working toner bath.

For the fixer of the first liquid toner from about 0.05 g. to about 5.0gs.

For the dispersant of the first liquid toner from about 0.025 g. toabout 5.0 gs.

For the pigment of the first liquid toner from about 0.025 g. to about5.0 gs.

For the charge director of the first liquid toner from about 0.0005 g.to about 0.5 g.

For the complex amphipathic molecule of the second liquid toner wherethe same includes a dye or pigment either chemically reacted therewithor bonded thereto or affiliated therewith by surface adsorption forcesfrom about 0.03 g. to about 30 g.

For the complex amphipathic molecule of the second liquid toner wherethe same does not include a color agent reacted or associated therewithfrom about 0.03 g. to about 30 g.

For the color agent of the second liquid toner where the same is notreacted or bound to the complex amphipathic molecule from about 0.03 g.to about 30 g.

For the charge director of the second liquid toner from about 1 ×10.sup.⁻⁶ g. to about 10 g.

The balance of each toner constitutes the liquid carrier.

Examples of different specific embodiments of the second liquid tonersfollow:

The first nine examples are examples of precursors, i.e. examples of theformation of the backbone, that is to say, the spine, of the amphipathicmolecule with which a subsequent reaction will later be described infurther examples which deal with the formation of the latices from theprecursors and toners from the latices.

EXAMPLE XI

In a clean dry 8 oz. glass jar is placed 100 gs. of2-ethylhexyl-acrylate and 1 g. of AZBN (azobisisobutyronitrile), apolymerization initiator. The jar is placed in a water bath maintainedat 75°±2° C. After about 30 minutes an exothermic polymerization takesplace. The temperature reaches a maximum of 120° C. in about 5 minutesafter the start of the exotherm. After it cools down to 90° C. the jaris removed from the water bath, loosely covered and placed in a hot airoven at 90° C. overnight to complete the polymerization. The product isa nearly waterwhite heavy syrup.

EXAMPLE XII

Four hundred grams of petroleum ether (b.p.90° -120° C) is placed in a 1liter reaction flask equipped with a stirrer, a thermometer, a refluxcondenser, and a dropping funnel and heated to a gentle reflux atatmospheric pressure. A solution of 1.2 g. AZBN in 200 g. of2-ethylhexyl-acrylate and 6 g. of glycidyl methacrylate is placed in thedropping funnel and allowed to drip into the reflux stream at such arate that the addition takes 3 hrs. The mixture is refluxed atatmospheric pressure for an additional 2 hrs. at which time 4 g. ofacrylic acid, 0.14 g. of 2, 6-di-tertiary butylphenol and 1 g. of lauryldimethyl amine is added. The mixture is refluxed at atmospheric pressurefor 12 more hours under a nitrogen blanket to esterify ca. 25% of theglycidyl rings of the copolymer. The product is a straw-colored somewhatviscous liquid.

EXAMPLE XIII

In a 500 ml. resin reactor equipped with a stirrer, a thermometer, areflux condenser and a dropping funnel is placed 250 gms. of Isopar E.The solvent is heated to 93°±1° C. and 250 gs. of 2-ethylhexyl acrylatecontaining 1.5 gs. of AZBN is added dropwise to the hot solvent over aperiod of 3 hrs. The mixture is maintained at 93° ± 1° C. for 3additional hours to complete polymerization. All reactions take place inthe reactor at atmospheric pressure. The product is a slightly viscousstrawcolored liquid.

EXAMPLE XIV

In a 1 liter reaction flask equipped with a stirrer, a thermometer and areflux condenser is placed 400 gs. of petroleum ether (b.p.90°-120° C.)and the same is then heated at atmospheric pressure to a moderate rateof reflux. A solution is made of 194 gs. lauryl methacrylate, 6.0 gs. ofglycidyl methacrylate and 3.0 gs. of benzoyl peroxide paste (60% by wt.in dioctyl phthalate) and placed in a 250 ml. dropping funnel attachedto the reflux condenser. The monomer mixture is allowed to drip into therefluxing solvent at such a rate that it requires 3 hrs. for the totalamount to be added. After refluxing 40 minutes at atmospheric pressurebeyond the final addition of monomer, 0.5 gs. of lauryl dimethyl amineis added and the refluxing is continued at atmospheric pressure foranother hour. Then 0.1 g. hydroquinone and 3.0 gs. methacrylic acid areadded and refluxing continued under a nitrogen blanket until ca. 52%esterification of the glycidyl groups is effected (about 16 hours). Theresulting product is a slightly viscous straw-colored liquid.

EXAMPLE XV

EXAMPLE XIV is repeated except that final refluxing is concluded whenca. 25% esterification of the glycidyl groups has been effected.

EXAMPLE XVI

In a 5 liter jacketed glass reactor open to the atmosphere and equippedwith a stirrer, a thermometer, a nitrogen bubbler and a reflux condenseris placed 2400 gs. of Isopar G. The solvent is heated to 110° ± 1° C. bycirculating hot triethylene glycol through the jacket. The temperatureof the glycol is controlled by a proportional heating unit with itstemperature sensor in a reservoir of the heating fluid from which thehot liquid is pumped to the reactor and subsequently returned to thereservoir for further heating. A three-way valve arrangement allows theglycol heating system to be isolated from the jacketed reactor so thatcold water can be immediately supplied to the jacketed reactor to keepthe temperature constant during the polymerization exotherm whennecessary. When the solvent reaches the forgoing temperature, a mixtureof 1035.7 gs. isodecyl methacrylate, 36.0 gs. glycidyl methacrylate and18.0 gs. Luperco ANS-50 (a paste consisting of 50% benzoyl peroxide byweight in dioctyl phthalate) is added at a constant rate over a 3 hr.period through a dropping funnel attached to the condenser. After all ofthe monomer solution has been added, the reaction mixture is held at110° ± 1° C. for another 30 min. Then 3.0 gs. lauryl dimethyl amine isadded and the reaction mixture again held at said temperture for 1 hr.At this point 0.6 gs. hydroquinone is added and the nitrogen bubbler isstarted to provide a nitrogen blanket during the esterification. Then18.0 gs. of methacrylic acid is added and the reaction temperature ismaintained until an acid drop indicates that 25% of the glycidyl ringshave been esterified (ca. 8 hrs.). The product that results is aslightly viscous straw-colored liquid.

EXAMPLE XVII

Using the same apparatus as described in EXAMPLE XVI, 1440 gs. of IsoparG is warmed to 110° ± 1° C. To this hot solvent, a solution of 1278.6gs. stearyl methacrylate, 32.4 gs. glycidyl methacrylate, and 16.2 gs.Luperco ANS 50 in 720 gs. of Isopar G is added through a dropping funnelattached to the condenser over a 3 hr. period, the temperature beingmaintained at 110° ± 1°0 C. After all of the monomer solution has beenadded, the reaction mixture is held at 110° ± 1° C. for another 40 mins.Then 2.8 gs. lauryl dimethyl amine is added and the reaction mixtureagain held at said temperature for 1 hour. At this point 0.54 gs.hydroquinone is added and the nitrogen bubbler is started to provide anitrogen blanket during the esterification. Then 16.2 gs. methacrylicacid is added and the reaction temperature is maintained until an aciddrop indicates that 24% of the glycidyl rings have been esterified (ca.7 hrs.). The product is a slightly viscous straw-colored liquid.

EXAMPLE XVIII

In a 500 ml. 3-neck round-bottom reaction flask open to the atmosphereand equipped with a stirrer, a thermometer, a thermocouple for athermoregulator and a reflux condenser, is placed 197.8 g. Isopar G. Thesolvent is warmed to 110° ± 1° C. with stirring. A mixture of 96.0 g.lauryl methacrylate, 3.0 g. glycidyl methacrylate, 0.74 gs. benzoylperoxide (99%), 50 mls. of benzene and 5.0 gs. ofp-phenylazoacrylanilide is prepared by stirring on a magnetic mixer for30 minutes at room temperature. Most by not all of thep-phenylazoacrylanilide dissolves. This mixture is added in 5 ml.increments at 5 min. intervals over a period of 3 hrs. to the solvent inthe flask. The mixture is kept well stirred so that each addition willbe identical in composition. After the last addition, the mixture isallowed to react at 110° ± 1° C. for 45 minutes and then 0.25 gs. lauryldimethyl amine is added. After one more hour of reaction time, 0.05 g.hydroquinone is added and a nitrogen sparge is started. Then 1.49 g.methacrylic acid is added and the temperature of the reaction mixture ismaintained at 110° ± 1° C. until the drop in acid value indicates that25% of the glycidyl rings have been esterified (ca. 6 hrs.). The batchis cooled to 50° C. and added slowly to 2700 mls. of methyl alcohol withcontinuous vigorous agitation. The precipitated polymer is allowed tosettle for 24 hours and is recovered by decantation. The polymer isair-dried at room temperature for 48 hours and then for 4 hours at 50°C. This polymer is then dissolved in 300 gs. of Isopar G giving a deepclear orange solution to be used in latex production.

EXAMPLE XIX

In a 500 ml. resin reactor equipped with a stirrer, a thermometer, areflux condenser open to the atomosphere, a nitrogen bubbler and adropping funnel is placed 197.8 gs. Isopar K and warmed to 110° ± 1° C.A mixture of 86.0 gs. lauryl methacrylate, 9.9 gs. N-1, 1, 3,3-tetramethyl butyl methacrylamide, 2.97 gs. glycidyl methacrylate and0.74 gs. benzoyl peroxide is placed in the dropping funnel and added tothe hot solvent at a constant rate over a 3 hr. period, the temperaturebeing maintained at 110° ± 1° C. The polymerization is allowed tocontinue for 6 more hours after the last of the monomer mixture has beenadded (a sample of the mixture analyzed to this time reveals a 96.4%polymerization). Then 0.12 gs. lauryl dimethyl amine is added to themixture and it is heated for another hour at which time 0.05 g.hydroquinone is added and a nitrogen sparge begins. Next 1.49 gs.methacrylic acid is added and the temperature of the mixture maintainedat 110° ± 1° C until a check of the acid content indicates that 25% ofthe glycidyl rings have been esterified (ca. 9 hrs.). The product is asomewhat viscous, straw-colored liquid.

LATICES

The following are examples of latices for the second liquid toneremploying those of the foregoing precursors which yield better results.

EXAMPLE XX

In a 500 ml. resin reactor open to the atmosphere, and equipped with astirrer, a thermometer and a reflux condensor, is placed 360 g. IsoparK, 185 gs. vinyl acetate, 30 gs. of the precursor prepared according toEXAMPLE XIV, 15 gs. methyl hydrogen maleate and 4 gs. AZBN. Thetemperature of the reaction mixture is raised to 85°±2° C. and heldthere for 4 hours. An additional 2 gs. of AZBN is then added to themixture and the polymerization is carried out for another 4 hours at 85°± 2° C. A thin blue white latex is obtained with a particle size of 0.04to 0.2 microns.

EXAMPLE XXI

A mixture of 27.5 gs. of the precursor solution prepared according toEXAMPLE XV, 30 g. methyl methacrylate, 0.5 g. methacrylic acid and 0.4g. AZBN is charged along with 134 g. petroleum ether (b.p. 60°-90° C.)and 29.5 g. Isopar G into a 500 ml. resin reactor open to the atmosphereand is gently refluxed for 20 minutes. Then 1.4 g. of a 10% solution byweight of n-octyl mercaptan in Isopar K is added to the reactor. Amixture of 166. g. methyl methacrylate, 3.4 g. methacrylic acid, 3.0 g.of the 10% solution of n-octyl mercaptan in Isopar K, and 0.4 g. AZBN isdripped at a constant rate into the stream of the gently refluxingcondnesor over a period of 21/2 hours. Gentle reflux is continued foranother 1/2 hour and the batch is then cooled to room temperature. Theresulting product is a smooth, white, slightly viscous latex with aparticle size of 0.4-1.0 microns.

EXAMPLE XXII

In a 2 liter 3-neck round-bottom flask open to the atmosphere andequipped with a stirrer, a thermometer, and a reflux condenser is placed848.5g. Isopar K, 70.7 g. of the precursor solution prepared accordingto EXAMPLE XVIII, 471.4 gs. vinyl acetate and 9.4 g. AZBN. The reactionmixture is heated with constant agitation to 86° C. and the temperatureis maintained for 4 hours. The resulting product is a light lemon yellowlatex with a particle size less than 0.2 micron and a solids content of31.7%.

EXAMPLE XXIII

A mixture of 18 g. of the precursor solution prepared according toEXAMPLE XV, 110 g. hydroxypropyl methacrylate, 3 g. AZBN and 200 g.Isopar K is placed into a 500 ml. resin reactor open to the atmosphereand heated with constant agitation. The exotherm begins at 78°-80° C.and the temperature rises to a maximum of 120° C. and then drops back to80° C. Polymerization is complete in 30 minutes. A slight amount ofover-size large particle material is removed by pouring the mixturethrough a 200 mesh nylon screen. A white latex of 0.5 micron particlesize is obtained. EXAMPLE XXIV

A solution of 15 g. of Bakelite Union Carbide poly (vinyl ethyl ether)(vinylite EDBM, a poly(vinyl) ethyl ether) with a reduced viscosity of4.0± 0.5 as determined by using 0.1 g. polymer in 100 mls. benzene at20° C., sp.gr. 0.968 at 20° C.) in 285 g. of Isopar G is made in a 500ml. resin reactor open to the atmosphere through a reflux condenser byshaving the resin into small particles and agitating it in the solventat 90° C. for 20 hours. The solution is cooled to room temperature and185 g. vinyl acetate and 2.0 g. benzoyl peroxide (99%) is added. Thebatch is heated until reflux occurs (ca. 95° C.) and the temperature ismaintained for 4 hours. After 45 minutes of heating at said temperature,the solution becomes turbid. After 1 hr. 15 mins. of heating at saidtemperature the batch becomes so viscous that although the stirrercontinues to run, no agitation is visible and the product appears to bea thick white cream. After 2 hours of heating at said temperature thebatch begins to thin and at the end of 3 hours of such continued heatingit thins to the consistency of heavy cream where it remains. At the endof the 4 hours, the dropwise addition of a solution of 1.5 g. lauroylperoxide in 30 gs. Isopar G is begun and completed over a 3 hour periodwhile the temperature of the system in maintained at 95° ± 2° C. Themixture is held at this temperature for 3 more hours after the last ofthe lauroyl peroxide solution has been added. The result is a whitelatex of 0.7-1.5 micron particle size.

EXAMPLE XXV

A mixture of 180 g. Isopar K, 100 gs. vinyl acetate, 15 gs. precursorsolution prepared according to EXAMPLE XVI, and 2 gs. AZBN is placed ina 500 ml. reaction flask equipped with a thermometer, a stirrer, areflux condenser and an internal cooling coil. The reacting mixture isheated to and maintained at 86° ± 2° C. for 4 hours with continuousagitation. The flask is open to the atmosphere through the cooled refluxcondenser. Occasionally it is necessary to cool the reacting mixture byrunning water through the cooling coil during the early stages of thereaction. The resulting product is a thin white to blue-white latexwhose particles are too small to be viewed in an optical microscope. Thelatex contains 33% solids.

EXAMPLE XXVI

In a 5 liter jacketed glass reactor equipped with a thermometer, astirrer, and a reflux condenser (the apparatus of EXAMPLE XVI) is placed2160 gs. Isopar K, 180 gs. precursor prepared according to EXAMPLE XV,1140 gs. vinyl acetate, 60 gs. N-vinyl-2-pyrrolidone and 24 gs. AZBN.The reaction mixture is heated to and maintained at 86° ± 2° C. for 4hours. The resulting product is a thin white to blue-white latex whoseparticles are too small to be viewed in an optical microscope.

EXAMPLE XXVII

In a 500 ml. resin reactor open to the atmosphere and equipped with astirrer, a thermometer and a reflux condensor is placed 360 gs. IsoparK, 190 gs. vinyl acetate, 30 gs. of the precursor prepared according toEXAMPLE XV, 10 gs. crotonic acid and 4 gs. AZBN. The temperature of thereaction mixture is raised to 85° ± 2° C. and held there for 4 hours. Anadditional 2 gs. of AZBN is then added to the mixture and thepolymerization is carried out for another 4 hours at 85° ± 2° C. A thinwhite latex is obtained

EXAMPLE XXVIII

In a 500 ml. resin reactor open to the atmosphere and equipped with astirrer, a thermometer, a thermoregulator, a reflux condenser and aninternal cooling coil is placed 40 gs. Lube Oil Additive 564, 284 gs.Isopar K and 2.2 gs. benzoyl peroxide (99%). With continuous agitation,the batch is heated to 80° C. and maintained at that temperature for 2hours. At this time a mixture of 10 gs. crotonic acid and 190 gs. vinylacetate is added all at once to the reacted precursor which has become adark amber. When the temperature of the reaction mixture has returned to80° C., AZBN is added to the mixture in 0.5 g. increments at 10 min.intervals until a total of 4.6 gs. has been added (3 hrs. 40 min.). Thereaction mixture is maintained at 80°±2° C. for 2 hours after theaddition of the AZBN is complete. A white latex is obtained of 35.7%solids with a particle size <0.3 micron.

EXAMPLE XXIX

An example of a dyeing procedure for a latex in which it is believedthat the dye does not react with the latex (although it is possible thatit may be associated therewith by hydrogen bonding) is a mixture of 10%by weight Sudan Orange RA (Solvent Yellow 14, C.I. No. 12055) in IsoparK the same being ball milled for 4 hours. Twenty gs. of this dispersionis added to 100 gs. of the latex prepared according to EXAMPLE XXVII andthe mixture is heated at 130°-135° F. for 8 hours with constantmechanical agitation. The mixture is filtered through a 200 mesh nyloncloth and allowed to cool to room temperature. A golden orange-coloredlatex is obtained.

SECOND LIQUID TONERS

The following are typical examples of second liquid toners inconcentrated form employing some of the foregoing latices.

EXAMPLE XXX

One hundred gs. of the latex produced in EXAMPLE XXVIII is placed in a500 ml. 3-neck round-bottom open top flask equipped with a stirrer, areflux condenser and a thermometer, and 2 gs. of Victoria Blue Base BA(C.I. No. 44045B) is added to it. The temperature is raised to 80°±5° C.and held there for 2 hours. The blue latex which results is cooled andfiltered through a 200 mesh nylon cloth to remove residual dye. To thiscolored latex there is added 2.5 gs. of a 1% by weight solution ofaluminum 3,5-diisopropylsalicylate in Isopar K to form a tonerconcentrate. Four gs. of this dyed latex is diluted with 2000 mls.Isopar K to form a working toner bath. This latex is a complex moleculeincluding in addition to the solvated and non-solvated polymericmoieties (in the liquid solvent system) a color agent moiety. The chargedirector is a separate compound. When used by itself as a toner bath ina Dennison Standard Book Copier, blue prints are obtained.

EXAMPLE XXXI

To the batch of latex as prepared in EXAMPLE XXVII is added 13.65 gs.Victoria Blue Base BA and the temperature of the mixture is maintainedat 85°±2° C. for 3 hours. The dark blue latex is filtered through a 200mesh nylon cloth and cooled to room temperature. To this colored latexthere is added 25 gs. of a 1% solution of the aluminum salt of3,5-di-t-butyl gamma resorcylic acid in Isopar G to form a tonerconcentrate. This toner concentrate likewise represents an example of acolor agent moiety which is part of a complex amphipathic polymericmolecule. Four gs. of this concentrate is added to 2000 mls. Isopar G toform a working toner bath. This toner bath in a Dennison Standard BookCopier, gives intense, bright blue images.

EXAMPLE XXXII

To the batch of latex as prepared in EXAMPLE XX is added 6.8 gs.Auramine O and 6.8 gs. Rhodamine and the temperature of the mixture ismaintained at 85°±2° C. for 3 hours. The now bright yellow-orange latexis filtered through a 200 mesh nylon cloth and cooled to roomtemperature. To this colored latex there is added 10 gs. of a 1%solution of the aluminum salt of 3,5 di-butyl gamma resorcylic acid inIsopar G to form a toner concentrate. This toner concentrate likewiserepresents an example of a color agent moiety which is part of a complexamphipathic polymeric molecule. Ten gs. of this concentrate is added to2000 mls. Isopar G to form a working toner bath. This mixture, when usedby itself as a toner bath in a Scott 3D Copier, gives extremely brightorange images.

EXAMPLE XXXIII

To the bath of latex as prepared in EXAMPLE XX is added 13.65 gs.Victoria Green and the temperature of the mixture is maintained at85°±2° C. for 3 hours. The now dark bluish green latex is filteredthrough a 200 mesh nylon cloth and cooled to room temperature. To thiscolored latex there is added 40 gs. of a 1% solution of the aluminumsalt of 3,5-di-t-butyl gamma resorcylic acid in Isopar G to form a tonerconcentrate. This toner concentrate likewise represents an example of acolor agent moiety which is part of a complex amphipathic polymericmolecule. Four gs. of this concentrate is added to 2000 mls. Isopar G toform a working toner bath. This mixture, when used by itself as a tonerbath in a Dennison Standard Book Copier, gives intense, bright bluishgreen images.

EXAMPLE XXXIV

Three gs. of the latex prepared according to EXAMPLE XXV are groundtogether with 0.25 gs. of Raven 11 in a mortar and pestle, has added toit 30 drops of a 1% solution of the aluminum salt of 3,5-di-t-butylgamma resorcylic acid and is thinned with a little Isopar K to form atoner concentrate. The concentrate is diluted to a volume of 2000 mls.with Isopar K to form a working toner bath. When this suspension is usedby itself as a toner bath in a Dennison Standard Book Copier, good blackprints are obtained.

EXAMPLE XXXV

To the batch of latex as prepared in EXAMPLE XXVII is added 13.65 gs.Crystal Violet (C.I. No. 42555B) and the temperature of the reactionmixture is maintained at 85°±2°C. for 3 hours. The colored latex isfiltered through a 200 mesh nylon cloth and cooled to room temperature.To this colored latex there is added 0.05 aluminum dresinate to form atoner concentrate. This toner concentrate likewise represents an exampleof a color agent moiety which is part of the complex amphipathicpolymeric molecule. Three gs. of this latex is added to 2000 mls. IsoparK to form a working toner bath. This bath, when used by itself in an A-MSunbeam 500 Copier, gives very good violet prints.

EXAMPLE XXXVI

To the batch of latex as prepared in EXAMPLE XXVII is added 13.65 gs.Megenta (C.I. No. 42510B) and the temperature of the reaction mixture ismaintained at 85°±2° C. for 3 hours. The colored latex is filteredthrough a 200 mesh nylon cloth and cooled to room temperature. To thiscolored latex there is added 0.05 g. aluminum dresinate and 20 gs. of a10% solution of Aerosol OT in Isopar K to form a toner concentrate. Thistoner concentrate likewise represents an example of a color agent moietywhich is part of the complex amphipathic polymeric molecule. Three gs.of this latex is added to 2000 mls. Isopar G to form a working tonerbath. When used by itself as a toner bath in a Dennison Standard BookCopier, magenta prints are obtained.

EXAMPLE XXXVII

Four gs. of the latex produced according to the EXAMPLE XXIX has addedto it 20 drops of a 1% solution of aluminum diisopropyl salicylate inIsopar G to form a toner concentrate. Said concentration when dilutedwith 2000 mls. Isopar K forms a working toner bath. This mixture, whenused by itself as a toner bath in a Dennison Standard Book Copier, givesyellowish-orange images.

All but one of the foregoing examples of second liquid toners have but asingle color agent. Optionally, plural color agents may be used, and itis usually preferred to employ two or more color agents, the conjointaction of which is to produce a deep color such, for example, as abrown-black, blue-black or purple-black.

The preparation of the second liquid toner can be carried out in stillanother fashion, although it still involves, of course, the use of amulti-functional complex polymeric molecule having a polymeric moietysolvated by and a polymeric moiety unsolvated by the liquid solventsystem; this is to form the amphipathic polymer polymeric molecule in asolvent in which such molecule is completely solvated and then by addinganother solvent which is a non-solvent for a polymeric moiety of thepolymer but is miscible with the first solvent, and desolvating thispolymeric moiety of the amphipathic polymer polymeric molecule whilesaid desolvated polymeric moiety remains bonded to the solvatedpolymeric moiety of the polymer, i.e., remains as a part of the polymer.If desired, all or a part of the first solvent can then be withdrawn.This is an extremely easy general way for obtaining a block amphipathicpolymer as the dispersed phase in accordance with the present invention.As an example of the foregoing a block polymer ofpolyisoprene-polystyrene-polyisoprene is formed by anionicpolymerization.

EXAMPLE XXXVIII

9.2 gs. of styrene are added to 60 cc. of tetrahydrofuran containing 3.3× 10.sup.⁻⁴ mole of sodium naphthalene (a catalyst) at -80° C. in athree-neck round bottom flask equipped with a mechanical stirrer, athermometer and a nitrogen inlet in a dry ice bath. The reaction iscompleted in 15 minutes, resulting in the formation of a "living"polystyrene polymer. Upon completion of polymerization 6.3 gs. ofisoprene is added (still at -80°C.) and the isoprene polymerizes on theliving ends of the polystyrene to form a block polymer. The now livingends of this block polymer, which block polymer is solvated by thetetrahydrofuran, are then grafted on to a suitable backbone polymer asby reacting at room temperature with 3 gs. of the precursor solution ofEXAMPLE XVIII to form the amphipathic polymer. Said backbone (precursor)polymer likewise is solvated by the tetrahydrofuran and such polymer ismade the solvated phase of a non-solvent for the block polymer of thesystem. Thereby the block polymer moiety is desolvated. The non-solventemployed is OMS which is added at room temperature to the solvated poly(styrene/isoprene)/poly (lauryl methacrylate - glycidyl methacrylate -methacrylic acid -- p-phenylazoacrylanilide) amphipathic polymer to forma latex. To this colored (golden-yellow) latex is added 2 gs. of a 1%solution of the aluminum salt of 3,5-di-t-butyl gamma resorcylic acid toform a toner concentrate. Fifteen gs. of the concentrate is diluted with2000 mls. of OMS to form a working toner bath. When this toner isemployed by itself as a toner bath in a Dennison Standard Book Copiergood yellow prints are obtained.

EXAMPLE XXXIX

One hundred grams of the latex produced in EXAMPLE XXVII is placed in a500 mls. 3-neck round bottom open top flask equipped with a stirrer, areflux condenser and a thermometer, and 1.2 gs. of Victoria Green (C.I.No. 42000B), 2.4 gs. Bismarck Brown (C.I. No. 21010B) and 0.3 g.Rhodamine Base (C.I. No. 45170B) are added to it. The temperature israised to 80°±5° C. and held there for two hours. The black latex whichresults is cooled and filtered through a 200 mesh nylon cloth to removeresidual dye. To this colored latex is added 5 mls. of aluminumdresinate solution, 10% by weight in Isopar H, to form a tonerconcentrate. To form a working toner bath, six grams of this concentrateis diluted with 2000 mls. Isopar H. When used by itself as a toner bathin a Dennison Standard Book Copier, dense black prints are obtained.

EXAMPLE XL

To 100 grams of the latex prepared in EXAMPLE XXV is added 5 mls. of a1% solution by weight of aluminum 3,5-diisopropylsalicylate in Isopar Gto form a toner concentrate. To use this concentrate as a developer, 4grs. thereof are added to 2000 mls. Isopar G. When tested in a copier,such as the Scott 3D, images are obtained which are shiny and visible bylight reflected at an acute angle from the image.

To prepare a hybrid toner embodying the present invention either of twoprocedures preferably is employed. One is, as indicated previously,simply to mix together a previously prepared liquid toner and apreviously prepared second liquid toner. Said liquid toners can beincorporated in the hybrid toner over a wide range of proportionsvarying from about 1/2 % to 99.5% of either liquid toner with theremainder being the other liquid toner. Any suitable mixing equipment,either mechanical or manual, can be employed. The other method ofpreparation is to mix together with a suitable liquid carrier all of thevarious constituents which, if properly segregated, would form the firstand second liquid toners.

At this time, it should be reiterated that the hybrid toner preferablyutilizes a liquid carrier which is common to both the first and thesecond liquid toners, although this is not an absolute necessity, and iftwo separate solvent systems are employed they should be compatible.Moreover, preferably, although not necessarily, the same chargedirector(s) is (are) used for both toners. This makes it less likelythat the two toners will be non-compatible and also simplifies procedurewhere the hybrid toner is made by directly mixing together all of theconstituents thereof rather than by first preparing the first liquidtoner and the second liquid toner separately and then mixing themtogether. In addition, it should be observed that certain chargedirectors, when used in combination, exert a synergistic effect. Thesehave been found to be charge directors which are solvated in the solventsystem. The synergism is not necessarily desirable inasmuch as theeffect of the charge director peaks on the density vs. concentration ofcharge director curve and, therefore, because of the synergism theamounts of charge director, where two or more of these are employed,should be adjusted downwardly, such adjustment being within the skill ofworkers in the art and having to be selected differently for everymixture of such charge directors, and being further dependent upon theconcentration and kinds of pigments and color agents employed. In theexamples given subsequently where plural charge directors are given fora single hybrid toner, such adjustment to take synergistic effects intoaccount always has been made.

There are other considerations whic should be taken into account, towit, that the amphipathic molecule (latex) of the second liquid toner iscapable of functioning, at least in part, as a dispersant for the firstliquid toner so that it is within the ambit of this invention to omit orreduce the amount of any other dispersant for the first liquid toner,said complex molecule being sufficient with certain other constituentsof the first liquid toner to supply all or part of the necessarydispersing capability. The color agent of either of the two liquidtoners can be omitted even if a visible developed image is requiredinasmuch as one color agent can suffice to supply the necessaryvisibility. However, it usually is desirable for both toners to containcolor agents which, in the case of the amphipathic molecle, may be apolymeric moiety of the complex molecule. The same color agent can serveas the color agent for the two toners, e.g. as the color agent for thehybrid toner.

Set forth below in two sections are examples of hybrid toners embodyingthe present invention, the first section of examples constitutingmixtures of the first toner and the second toner which are prepared bymixing together pre-prepared first and second liquid toners. The secondconstitutes examples of hybrid toners prepared by mixing together theconstituents desired to be present in the finished hybrid toner butwithout the previous preparation of the first and second liquid tonersseparately from one another.

The amounts of the different non-carrier constituents of the hybridtoners are, like those of the first and the second liquid toners,capable of so wide a variation that it is not meaningful to give anyspecific ranges. However, as a guide, the following representapproximately maximum and minimum amounts of the various non-carrierconstituents per liter of liquid toner in a working hybrid toner bath.

For the fixer (as hereinbefore described) which is a separate chemicalcompound or composition (a chemical entity separate from the dispersant)from about 0.0025 g. to about 5 gs.

For the dispersant (as hereinbefore described) which is a chemicalcompound or composition that is chemically separate from the fixer fromabout 0.5 g. to about 5 gs. As to this dispersant it should be notedthat it may embrace the amphipathic molecule alone or in combinationwith other dispersants.

For the color agent from about zero g. to about 1.0 g. It should benoted that the absence of color agent is not particularly desirable butis envisioned that no color agent be present in the hybrid toner whenthe same is used in the preparation of a lithographic master.

For the charge director from about 1 × 10.sup.⁻⁶ g. to about 10 gs.

For the complex amphipathic polymeric molecule from about 0.05 g. toabout 30 gs.

The balance of the hybrid toner constitutes the solvent system.

EXAMPLES OF HYBRID TONERS FORMED BY MIXING PREVIOUSLY FORMED FIRST ANDSECOND LIQUID TONER CONCENTRATES AND DILUTING SAME EXAMPLE XLI

4.5 gs. of the first liquid toner concentrate of EXAMPLE VIII and 0.5 g.of the second liquid toner concentrate of EXAMPLE XXX are added to 2000mls. of Isopar G. The developer bath is either prepared manually andthen added to a copying machine or the components thereof are addedseparately to the developing tray of a copying machine such as, e.g. theSCM 44 Copier and mixed by the action of the circulating pump. Blackdense prints are obtained, free from background.

EXAMPLE XLII

0.5 g. of the first liquid toner concentrate of EXAMPLE VIII and 4.5 gs.of the second liquid toner concentrate of EXAMPLE XXX are added to 2000mls. of Isopar G to form a working toner bath. When tested in the SCM 44Copier, dense blue black prints are obtained.

EXAMPLE XLIII

In order to obtain a developer for use in the preparation oflithographic masters, add 8.0 gs. of the second liquid toner concentrateof EXAMPLE XXXIX and 0.04 g. of the first liquid toner concentrate ofEXAMPLE IX to 2000 mls. Isopar G. This developer gives excellent resultsin an office copy machine, such as the Scott 3-D copier.

EXAMPLE XLIV

In order to obtain a developer for use in the preparation of microficheimages, add 4.0 gs. each of the first and second liquid tonerconcentrates mentioned in EXAMPLE XLIII to 2000 mls. Isopar G.

EXAMPLE XLV

The addition of 0.04 gs. of the first liquid toner concentrate ofEXAMPLE X and 8.0 gs. of the second liquid toner concentrate of EXAMPLEXL to 2000 mls. of Isopar H gives a developer for the Toshiba BD-32Copier which gives excellent lithographic masters.

EXAMPLES OF HYBRID TONERS FORMED BY MIXING CONSTITUENTS WITH A SOLVENTSYSTEM DIRECTLY WITHOUT THE INTERMEDIATE STEPS OF INDEPENDENTLY FORMINGTHE FIRST AND SECOND LIQUID TONERS EXAMPLE XLVI

Ball mill the following ingredients together for 23 hours at 90° F.

    ______________________________________                                        100      gs.        Dymerex                                                   50       gs.        Pliolite VTAC-L                                           60       gs.        Toner 8100                                                500      gs.        Solvent 460                                               ______________________________________                                    

Then add 100 gs. Solvent 460 and ball mill at the same temperature foran additional hour. To 145 gs. of the foregoing add 60 gs. of the latexof EXAMPLE XXV (in addition to its functions as a major constituent ofthe second liquid toner component, this latex acts as a dispersent forthe constituents of the first liquid toner component) and 0.75 g. ofaluminum stearate and ball mill for 18 hours at 90° F. to form a hybridtoner concentrate. 5 gs. of the hybrid concentrate is diluted with 2000mls. Isopar K to form a working hybrid toner bath which when used in aDennison Mark I Book Copier produces dense black prints, free frombackground.

Although in this specific example, the two toner components are ballmilled together at a somewhat elevated temperature, the majority ofhybrid toners formed by blending of mixtures of first and second liquidtoners are prepared by simple manual or automatic agitation means atambient temperatures.

                  EXAMPLE XLVII                                                   ______________________________________                                        20         gs.    Dymerex                                                     10         gs.    Pliolite VTAC-L                                             8          gs.    GAF Black M Toner                                           120        gs.    Solvent 460                                                 1          g.     Aluminum stearate                                           30         gs.    Latex of EXAMPLE XXV                                        ______________________________________                                    

The above ingredients are ball miled at 90° F. for 18 hours to form ahybrid toner concentrate. To prepare the working hybrid toner bath, 5gs. of hybrid toner concentrate is dispersed in 2000 mls. isopar K. Whenused in a Dennison Mark I Book Copier, dense black prints are obtainedfree from background. Note that the latex also acts as a dispersant forthe pigment and the charge director.

                  EXAMPLE XLVIII                                                  ______________________________________                                        20         gs.    Dymerex                                                     10         gs.    Pliolite VTAC-L                                             15         gs.    GAF Black M Toner                                           120        gs.    Solvent 460                                                 2          gs.    Lube Oil 564                                                1          g.     Aluminum stearate                                           30         gs.    Latex of EXAMPLE XXV                                        ______________________________________                                    

The above ingredients are ball milled at 90° F. for 18 hours to form ahybrid toner concentrate. When used at a concentration of 5 gs./2000mls, Isopar G in a Savin 220 Copier, dense black prints are obtained,free from background.

                  EXAMPLE XLIX                                                    ______________________________________                                        25        gs.    Staybelite                                                   80        gs.    Latex of EXAMPLE XXXIX                                       12        gs.    Toner 8100                                                   3         gs.    Spirit Nigrosine SSB                                         6         gs.    Raven 11                                                     1         g.     Aluminum stearate                                            20        gs.    Alkanol DOA                                                  50        gs.    Isopar G                                                     ______________________________________                                    

The above formula is ball milled for 40 hours at ambient temperature toform a hybrid toner concentrate. When used in a Scott 3D Copier at aconcentration of 4gs./2000 mls. Isopar G, dense black background-freeprints are obtained.

                  EXAMPLE L                                                       ______________________________________                                        25        gs.    Staybelite                                                   6         gs.    Latex of EXAMPLE XXXIX                                       12        gs.    Toner 8100                                                   3         gs.    Spirit Nigrosine SSB                                         6         gs.    Raven 11                                                     2         gs.    Aluminum stearate                                            20        gs.    Alkanol DOA                                                  50        gs.    Isopar G                                                     ______________________________________                                    

The above formula is ball milled for 40 hours at ambient temperature toform a hybrid toner concentrate. When used in a Savin 200 Copier at aconcentration of 6 gs./2000 mls. Isopar G, dense black background-freeprints are obtained.

                  EXAMPLE LI                                                      ______________________________________                                        25    gs.     Staybelite                                                      80    gs.     Latex of EXAMPLE XX dyed with Victoria                                        Blue BA Base, 4% by weight                                      8     gs.     Toner 8100                                                      2     gs.     Spirit Nigrosine SSB                                            4     gs.     Statex B-12                                                     10    gs.     Alkanol DOA                                                     10    gs.     Polymerized castor oil                                          ______________________________________                                    

The above ingredients are ball milled at 98° F. for 30 hours. The outputis cut with a mixture of:

    ______________________________________                                        0.75        g.    Aluminum stearate                                           10          gs.   Polymerized castor oil                                      50          gs.   Isopar K                                                    ______________________________________                                    

and ball milled for an additional hour to form a hybrid tonerconcentrate. When used at a concentration of 3 gs./2000 mls. Isopar K ina Dennison Mark I Book Copier, dense black background-free prints areobtained.

                  EXAMPLE LII                                                     ______________________________________                                        950    gs.     Latex of EXAMPLE XX dyed with                                                 Victoria Blue BA Base, 4% by weight                            20     gs.     Staybelite                                                     8      gs.     Toner 8100                                                     2      gs.     Spirit Nigrosine SSB                                           4      gs.     Raven 11                                                       8      gs.     Alkanol DOA                                                    8      gs.     Polymerized castor oil                                         ______________________________________                                    

The above ingredients are ball milled at 100° F. for 40 hours. When usedat a concentration of 25 gs./2000 mls. Isopar G with the addition of 10drops of a 1% solution by weight in Isopar G of the aluminum salt of 3,5diisopropylsalicylic acid, in a Toshibafax BD-32 Copier, excellentlithographic masters are produced.

With the use of the novel hybrid toner three unusual effects have beenobserved in connection with the preparation of developed images whichare to be used as lithographic masters after etching.

The first of these concerns the "fill" which is the uniformity ofelectrostatographic deposit over a solid colored area in such aproportion that it is a reasonable facsimile of the original imagedensitywise. It will be recalled that, using the first liquid toneralone, the fill inwardly of the periphery of a colored zone ofreasonably large size was poor. However, when even small amounts, e.g.as low as 1/2%, of the constituents of the second liquid toner arepresent in the hybrid liquid toner the fill is sharply bettered. Therate of improving the fill tapers off as larger amounts of theconstituents of the second liquid toner are employed, and if this werethe sole desideratum, it would be desirable not to include predominantamounts or even large amounts of the second liquid toner or itsconstituents in the hybrid liquid toner for economical reasons solely,inasmuch as the cost of the amphipathic molecule exceeds the cost of thefixer and dispersant of the first liquid toner. However, there are otherconsiderations which will be mentioned below which govern the ratio ofthe constituents of the two liquid toners in the hybrid toner and it isobserved that the use of larger amounts of the constituents of thesecond liquid toner in the hybrid toner do not lessen the effect ofimprovement in fill. Heretofore it has been proposed to use varioustypes of mechanical approaches to the solution of this problem such, forinstance, as the addition of development electrodes submerged in thebath and adjacent the path of travel of the immersed sheet carrier, butthe results obtained thereby were largely unsatisfactory, and the factthat such samll amounts of a second liquid toner in the hybrid toner soeasily provides the desired fill was entirely unexpected. There is noexplanation for such phenomenon, that is to say, the influence of theamphipathic polymeric molecule on the density of deposit of the pigmentparticles of the first liquid toner on an electrostatic latent image.

Another important improvement resulting from the combination of the twotoners and, specifically, the addition of the constituents of the secondliquid toner to the first liquid toner, is the lengthening of the lifeof the developed image when employed as a lithographic master. It hasbeen found that, despite the short life of lithographic masters preparedwith the first type of liquid toner, the life of a lithographic masterprepared with the hybrid toner is very substantially greater and,indeed, at least as great as the life of the lithographic masterprepared solely with the second liquid toner; in other words, the mixingtogether of the two liquid toners for the purpose of increasing filldoes not degrade the life of the lightographic master prepared with thehybrid toner below the life of the lithographic master prepared with thesecond liquid toner alone so that, by this invention, both the fill andthe length of life of a lithographic master can be bettered. In order tosecure usable results insofar as the length of the life of alithographic master is concerned, it is desirable to employ not lessthan about 1 part of the constituents of the second liquid toner toabout 20 parts of the constituents of the first liquid toner. Inconnection with the foregoing it will be appreciated that theseproportions may be adjusted depending upon the length of life desiredand the cost factors involved; that is to say, if it is known that for aparticular use a less than very lengthy life is required of alithographic master, it would be a needless extravagance to use more ofthe constituents of the second liquid toner than will produce such anextended life.

An additional advantage observed by employing the constituents of boththe first and the second liquid toners in a hybrid toner either for usein preparing a lithographic master or for general office copyingpurposes is that the presence of even small amounts of the constituentsof the first liquid toner very substantially increases the edge contrastof a developed image, in other words, the sharpness or snappiness of thedeveloped image. Such improvement in edge contrast is noticeable witheven amounts as small as 1/2% of the constituents of the first liquidtoner in the hybrid toner. However, again, the matter of economicalconsiderations usually will preclude the employment of very largeamounts of the constituents of the second liquid toner. Nevertheless,this increase in sharpness is not destroyed by using larger amounts ofthe constituents of the first liquid toner in the hybrid toner.

A further advantage has been observed which results from the presence ofeven small amounts of the constituents of the second liquid tonner inthe hybrid toner, this relating to the resistance of the deposited imageto the etching solvent. It is characteristic of images deposited throughemployment of the first liquid toner that unless the original isextremely even in density the etch tends to attack lighter portions ofthe image and this results in portions of the image becoming lessoleophilic than other portions so that the copies prepared with thelithographic master experience loss of quality in comparison with theoriginal. But the addition of even very small amounts of theconstituents of the second liquid toner overcomes this drawback and itwill be observed that the developed images prepared with the hybridtoner have a substantial uniformity of resistance to transformation bythe etching solution from the oleophilic state to the hydrophilic state.This effect is not decreased by the presence of larger amounts of theconstituents of the second liquid toner in the hybrid toner.

The second special increased utility ensuing from the use of the hybridtoner concerns the electrostatographic preparation of microfiche images.Heretofore there has been no widely commercially acceptable toner forelectrostatographic creation of microfiche images. When the first liquidtoner was employed it was subject to the aforementioned difficulty thatthe fixer had to be raised to such elevated temperature during fusingthat it rendered the transparent thermoplastic carrier for thetransparent photoconductor dimensionally unstable. This resulted in therunning together or blurring of adjacent supposedly spaced portions ofthe reproduced image with such a high loss of resolution that such imagehad no commercial value. On the other hand, where the second liquidtoner was employed the edges of image portions were not faithfulreproductions of the corresponding edges of the original so that here,too, there was a tendency to lose resolution due to a wavering of theedges of the reproduction that was not present in the original. Oneother toner had been proposed for electrostatic creation of mmicroficheimages, which toner required several minutes for setting afterdevelopment. In the interim preceding hardening of the image, the tonercould not be touched and this was an impractical approach undermodernday labor conditions and particularly where high speedreproductions were involved. All of these defects have been overcomewhen the first and second liquid toners are conjointly used in a hybridtoner. For an unexplainable reason or reasons the presence of theconstituents of the first liquid toner has been found to cause the edgeportions of the developed image to be faithful facsimiles of the edgeportions of the original, this being true where even the minimal amountsabove mentioned of the first liquid toner are employed. Conversely, thepresence of even the minimal amounts of the second liquid toner havebeen found to enable the image to be fixed quickly and firmly attemperatures below those necessary for fixing the first liquid toner andbelow that which will render the thermoplastic transparent carrier foran organic transparent photoconductor dimensionally unstable. It is notknown whether this decrease in setting temperature is due to a lowerfusing point for the fixative moiety of the amphipathic molecule or tothe ability of the amphipathic molecule to form a solvent-induced bondwith the aforesaid thermoplastic carrier, or for some other reason notknown, but, be that as it may, the physical result is present and forthe first time enables a microfiche image to be created speedily and ata low enough temperature not to affect resolution so that the resolutioncapability of the final electrostatographically produced image will be afunction solely of the resolution obtainable with the original at theoptical reduction ratio employed and will in no wise be deleteriouslyaffected by the reproduction process.

It thus will be seen that there is provided a system which achieves thevarious objects of the invention and which is well adapted to meet theconditions of practical use.

As various possible embodiments might be made of the above invention,and as various changes might be made in the embodiments above set forth,it is to be understood that all matter herein described is to beinterpreted as illustrative and not in a limiting sense.

Having thus described the invention, there is claimed as new and desiredto be secured by Letters Patent:
 1. A liquid electrostatographic tonerconsisting essentially of a combination of:A. a first liquid tonerincludingi. a solvent system having an evaporation rate at least as fastas that of kerosene, but slower than that of hexane, and a Kauri-butanolnumber less than 35, is substantially aromatic-liquid-free, has anelectrical resistivity of at least about 10⁹ ohm centimeters, adielectric constant of less than three and one half and a Tagliabueclosed cup flash point of at least 100° F, is non-toxic and non-polar,has no objectionable odor, and has a viscosity of between 0.5 and 2.5centipoises at room temperature, Ii. a solid synthetic thermoplasticfixer dissolved in the solvent system and iii. a dispersant; B. a secondliquid toner includingi. a solvent system compatible with the firstliquid toner and which has an evaporation rate at least as fast as thatof kerosene, but slower than that of hexane, and a Kauributanol numberless than 35, is substantially aromatic-liquid-free, has an electricalresistivity of at least about 10⁹ ohm centimeters, a dielectric constantof less than three and one half and a Tagliabue closed cup flash pointof at least 100° F, is non-toxic and non-polar, has no objectionableodor, and has a viscosity of between 0.5 and 2.5 centipoises at roomtemperature, ii. an amphipathic polymeric molecule of the graft typehaving a polymeric backbone part and a polymeric graft part on saidbackbone part, said molecule being composed of two polymeric moieties ofwhich at least one is thermoplastic, said first polymeric moiety, whichis one of said parts, being solvated by said systems, a portion of saidfirst polymeric moiety being a fixative and a dispersant, and a secondpolymeric moiety, which is the other of said parts, being insoluble insaid systems, said second polymeric moiety having a particle sizebetween 25 mμ and 25μ, a portion of said second polymeric moiety being afixative, so that there is provided a continuous phase constituting thesolvent systems with the first polymeric moiety dissolved therein and adispersed phase constituting the non-solvated polymeric moiety wherebysaid molecule acts as a mono-dispersed particle phase, a fixative and adispersant; C. the first liquid toner being present in an amount of from0.5% to 99.5%, the balance of the liquid electrostatographic toner beingthe second liquid toner; and D. at least one of said liquid tonersincluding a charge director.
 2. A liquid electrostatographic toner asset forth in claim 1 wherein the second liquid toner further includes acolor agent.
 3. A liquid electrostatographic toner as set forth in claim2 wherein the color agent is a moiety of the amphipathic molecule.
 4. Aliquid electrostatographic toner as set forth in claim 2 wherein thecolor agent is a compound other than the amphipathic molecule.
 5. Aliquid electrostatographic toner as set forth in claim 1 wherein theamphipathic molecule includes a solvated polymeric moiety selected fromthe group consisting of: crepe rubber; refined linseed oil, degradedrubber; alkyd resins; polyisobutylene; polybutadiene; polyisoprene,polyisobornyl methacrylate; homopolymeric vinyl esters of long chainfattey acids; homopolymeric vinyl alkyl ethers; homopolymers of the C₄-C₂₂ alkyl esters of acrylic and methacrylic acid in a molecular weightrange of about 10³ to about 10⁶ ; copolymers of the aforesaid C₄ -C₂₂alkyl esters with one another; copolymers of the aforesaid C₄ -C₂₂ alkylesters with one another and with methyl, ethyl, isopropyl and propylesters of acrylic and methacrylic acids; copolymers of the C₄ -C₂₂ alkylesters of acrylic and methacrylic acids with monomers containing acrylicacid, methacrylic acid, crotonic acid, maleic acid, atropic acid,fumaric acid, itaconic acid, citraconic acid, acrylic anhydride,methacrylic anhydride, maleic anhydride, acryloyl chloride, methacryloylchloride, acrylonitrile, methacrylonitrile, N-vinyl pyrrolidone,acrylaminde and derivatives thereof, methacrylamide and derivativesthereof, hydroxyethyl methacrylate, hydroxyethyl acrylate, hydroxypropylmethacrylate, hydroxypropyl acrylate, dimethylaminomethyl methacrylate,dimethylaminomethyl acrylate, dimethylaminoethyl methacrylate,dimethylaminoethyl acrylate, diethylaminomethyl methacrylate,diethylaminomethyl acrylate, diethylaminoethyl methacrylate,diethylaminoethyl acrylate, t-butylaminoethyl methacrylate,t-butylaminoethyl acrylate, cyclohexyl acrylate, allyl alcohol andderivatives thereof, cinnamic acid and derivatives thereof, styrene andderivatives thereof, butadiene, methallyl alcohol and derivativesthereof, propargyl alcohol and derivatives thereof, indene andderivatives thereof, norbornene and derivatives thereof, vinyl ethers,vinyl esters, vinyl derivatives other than vinyl ethers and vinylesters, glycidyl methacrylate and acrylate, mono- and dimethyl maleate,mono- and diethyl maleate, mono-n-butyl maleate, mono-sec-butyl maleate,mono-ter-butyl maleate, monobenzyl maleate, mono-2-ethylhexyl maleate,mono-n-octyl maleate, mono- and dimethyl fumarate and mono- and diethylfumarate; condensation polymers; copolymers of butadiene, isoprene andisobutylene with c₄ -C₂₂ alkyl esters of acrylic and methacrylic acids;polycarbonates; polyamides; polyurethanes and epoxies, and thenonsolvated polymeric moiety comprises homopolymers and copolymersformed from monomers selected from the group consisting of vinylacetate, vinyl chloride, methyl acrylate, methyl methacrylate, ethylacrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate,isopropyl acrylate, isopropyl methacrylate, hydroxy ethyl acrylate,hydroxy ethyl methacrylate, hyydroxy propyl acrylate, hydroxy propylmethacrylate, acrylonitrile, methacrylonitrile, acrylamide,methacrylamide, acrylic acid, acrylic anhydride, methacrylic acid,methacrylic anhydride, mono methyl maleate, mono ethyl maleate,mono-n-butyl maleate, mono-sec-butyl maleate, mono-ter-butyl maleate,mono-2-ethylehexyl maleate, mono-n-octyl maleate, mono methyl fumarate,mono-ethyl fumarate, styrene, vinyl toluene, maleic acid, maleicanhydride, crotonic acid, crotonic anhydride, fumaric acid, atropicacid, allylamine, vinyl amine, allyl alcohol, vinyl pyridines andderivatives thereof, glycidyl acrylate, glycidyl methacrylate,dialkylaminoalkyl methacrylate, dialkylaminoalkyl acrylate, methacrylylacetone, N-hydroxymethyl methacrylamides, alkoxymethyl methacrylamides,acryloyl chloride, methacryloyl chloride, vinyl isocyanate,cyanomethylacrylate, vinyl β-chloroethylsulphone, vinyl sulphonic acid,monobenzyl maleate and vinyl phosphoric acid.
 6. A liquidelectrostatographic toner as set forth in claim 1 wherein theamphipathic molecule includes a backbone chain of comonomers andattached chains having attached sites of a precursor monomer derivedfrom monomers selected from the affiliated monomer groups set forthbelow:

    ______________________________________                                                          Attached site precursor                                                       monomer                                                                       (one or more non-mutually                                                     reactive                                                    Comonomer         radicals to be selected from                                of backbone chain each group)                                                 ______________________________________                                                              Acrylic acid                                                                  Methacrylic acid                                        Glycidyl methacrylate or                                                                            Maleic acid                                              acrylate      --     Fumaric acid                                                                  Atropic acid                                                                  Allylamine                                                                    Vinyl amine                                                                   Hydroxylethyl methacrylate                                                     and acrylate                                                                 Hydroxypropyl methacrylate                                                     and acrylate                                           Acryloyl or methacryloyl                                                                     --     Acrylamide                                               chloride             Methacrylamide                                                                Allyl alcohol                                                                 Allylamine                                                                    Vinyl amine                                             Acrylic acid          Vinyl pyridines                                         Methacrylic acid      Glycidyl methacrylates                                  Maleic acid    --     Vinylamine                                              Crotonic acid         Allylamine                                              Alkyl hydrogen maleates                                                                             Dialkylaminoalkyl meth-                                 Alkyl hydrogen fumarates                                                                             acrylates and                                                                 acrylates                                                                    Allylamine                                              Vinyl isocyanate                                                                             --     Vinyl amine                                                                   Methacrylyl acetone                                     Cyanomethylacrylate                                                                          --     Vinyl amine                                                                   Allylamine                                                                    Allylamine                                              Vinyl β-chloroethyl-                                                                    --     Vinyl amine                                              sulphone             Allyl alcohol                                                                 Hydroxyalkyl methacrylates                                                    Glycidyl methacrylate                                   Methacrylic anhydride Vinyl amine                                             Acrylic anhydride                                                                            --     Allylamine                                              Maleic anhydride      Hydroxyalkyl methacrylates                                                    Allyl alcohol                                                                 N-hydroxymethyl                                         Vinyl sulphonic acid                                                                         --      methacrylamides                                        Vinyl phosphoric acid Alkoxymethyl                                                                   methacrylamides.                                       ______________________________________                                    


7. A liquid electrostatographic toner as set forth in claim 1 whereinthe charge director is selected from the group consisting of:di-2-ethylhexyl sodium sulfosuccinate; di-tridecyl sodiumsulfosuccinate; aluminum, chromium, zinc and calcium salts of3,5-dialkylsalicylic acid, wherein the alkyl group is propyl, isopropyl,butyl, isobutyl, tertiary butyl, amyl, isoamyl and other alkyl groups upto C-18; aluminum, chromium, zinc and calcium salts of dialkylgamma-resorcylic acid, wherein the alkyl is as above; isopropylaminesalt of dodecylbenzene sulfonic acid; aluminum, vanadium and tindresinates; cobalt, iron, lithium, tin and manganese octoates; apartially imidized polyamine with lubricating-oil solublepolyisobutylene chains and free secondary amines, gravity at 60° F. API22.9, specific 0.92, flash point by the Cleveland open cup method, 425°F., viscosity at 210° F., 400 SSU, color (ASTM D-1500) L55D, nitrogenpercentage by weight 2.0, and alkalinity value, (SM-205-15) 43; soyabean lecithin; aluminum salt of 50--50 by weight mixture of the mono-and di-2 ethylhexyl esters of phosphoric acid; zinc, lead, copper,cadmium, calcium, aluminum and iron stearates; zinc and aluminumpalmitates; aluminum oleate; copper, manganese, cobalt and leadlinoleates; manganese linoresinate; and 1-[2-hydroxyethyl]-2-[mixedpentadecyl and heptadecyl]-2-imidazoline.
 8. A liquidelectrostatographic toner as set forth in claim 1 wherein the solidsynthetic thermoplastic fixer is selected from the group consisting of:polymerized and hydrogenated thermoplastic acidic wood rosin, glycerolester of modified wood rosin, pentaerythritol ester of wood rosin,pentaerythritol ester of polymerized wood rosin, modifiedpentaerythritol ester of wood rosin, pentaerythritol ester ofhydrogenated wood rosin, pentaerythritol ester of dimeric resin acids,modified pentaerythritol ester of wood rosin, glycerol ester ofpolymerized wood rosin, a thermoplastic petroleum hydrocarbon resin inwhich the units of the polymer are predominantly selected from the groupconsisting of aromatic and cyclic units, having an acid number of lessthan 1 and a softening point of 100° C by the ring and ball method,fully hydrogenated glycerol ester of wood rosin, internally plasticizedpentaerythritol ester of wood rosin, dimeric resin acids, a vinyltoluene/acrylate copolymer, and a vinyl toluene/n-butylmethacrylate/stearyl methacrylate polymer.